ChemEngineering 03 00063 v2

chemengineering
Review
Metal Oxides Applied to Thermochemical
Water-Splitting for Hydrogen Production Using
Concentrated Solar Energy
Stéphane Abanades
Processes, Materials, and Solar Energy Laboratory, PROMES-CNRS, 7 Rue du Four Solaire, 66120 Font Romeu,
France; stephane.abanades@promes.cnrs.fr; Tel.: +33-0468307730

Received: 17 May 2019; Accepted: 2 July 2019; Published: 4 July 2019
Abstract: Solar thermochemical processes have the potential to efficiently convert high-temperature
solar heat into storable and transportable chemical fuels such as hydrogen. In such processes,
the thermal energy required for the endothermic reaction is supplied by concentrated solar energy
and the hydrogen production routes differ as a function of the feedstock resource. While hydrogen
production should still rely on carbonaceous feedstocks in a transition period, thermochemical
water-splitting using metal oxide redox reactions is considered to date as one of the most attractive
methods in the long-term to produce renewable H2 for direct use in fuel cells or further conversion to
synthetic liquid hydrocarbon fuels. The two-step redox cycles generally consist of the endothermic
solar thermal reduction of a metal oxide releasing oxygen with concentrated solar energy used as the
high-temperature heat source for providing reaction enthalpy; and the exothermic oxidation of the
reduced oxide with H2 O to generate H2 . This approach requires the development of redox-active and
thermally-stable oxide materials able to split water with both high fuel productivities and chemical
conversion rates. The main relevant two-step metal oxide systems are commonly based on volatile
(ZnO/Zn, SnO2 /SnO) and non-volatile redox pairs (Fe3 O4 /FeO, ferrites, CeO2 /CeO2−δ , perovskites).
These promising hydrogen production cycles are described by providing an overview of the best
performing redox systems, with special focus on their capabilities to produce solar hydrogen with
high yields, rapid reaction rates, and thermochemical performance stability, and on the solar reactor
technologies developed to operate the solid–gas reaction systems.
Keywords: hydrogen; solar energy; water-splitting; thermochemical; two-step cycles; redox materials;
metal oxides; solar fuel; solar reactor
1. Introduction
Solar thermochemical processes are efficient routes for converting high temperature solar heat
into valuable and sustainable chemical energy carriers (solar fuels). Thermochemical water-splitting
cycles consist of the thermal conversion of water into separate streams of hydrogen and oxygen via
a series of endothermic and exothermic chemical reactions. It is particularly attractive due to the
abundance, availability and low cost of the water feedstock. Endothermic reactions can be driven by
high-temperature concentrated solar thermal energy [1–4]. A thermochemical water-splitting cycle
operates at much lower working temperatures than direct water thermolysis while resulting in the
same global water decomposition reaction.
The interest in thermochemical water-splitting cycles boomed in the late 70s and early 80s with the
oil crisis [5–9], and most of the cycles were proposed for being combined with a primary nuclear energy
source, thereby imposing constraints on the operating temperature that should remain below 900 ◦ C.
Although several hundred cycles have been proposed, only a few has been subjected to substantial
ChemEngineering 2019, 3, 63; doi:10.3390/chemengineering3030063 www.mdpi.com/journal/chemengineering

ChemEngineering 2019, 3, 63 2 of 28
research, and the demonstration of technical feasibility and potential for high efficiency has been
barely carried out. In previous studies dealing with screening and evaluation of thermochemical
cycles, the maximum cycle temperature level corresponded to the deemed optimum for an advanced
high-temperature Generation IV nuclear reactor (e.g. high-temperature gas-cooled reactor HTGR,
very-high-temperature reactor VHTR), i.e. about 850 ◦ C [10]. Processes involving higher temperatures
were eliminated. A large research effort has mainly been focused on UT-3 and Iodine-Sulphur (I-S)
cycles [10–16], in which the primary energy input was the high-temperature heat released from an
advanced nuclear reactor (4th generation power station). These cycles have also been proposed in
combination with a solar energy source [17–22]. The medium temperature I-S and hybrid sulphur
(Westinghouse) cycles that may use either solar or nuclear heat have been examined (e.g., EU-projects
HYTHEC (FP6), HycycleS (FP7) and SOL2HY2 (FCH JU)). In particular, the solar decomposition
of H2 SO4 above 850 ◦ C involved in both cycles was studied [17]. Regarding the hybrid sulphur
cycle (Ispra Mark 11), sulphuric acid is decomposed in the first reaction at a high temperature to
generate sulphur dioxide and oxygen (that can be separated and valorized as byproduct). Sulphur
dioxide is then electrolyzed with water at about 80 ◦ C in the second reaction forming hydrogen
and fresh sulphuric acid to be recycled back to the first reaction. This electrolysis step requires only
about one tenth of the electrical power needed for conventional water electrolysis, thereby reducing
the global process energy demand for hydrogen production, which is crucial for future industrial
technology commercialization. However, such complex cycles operating below 1000 ◦ C usually involve
incomplete reactions or electrochemical steps (hybrid cycles), additional separation steps, hazardous
or corrosive reactants and/or products, which results in materials issues for reactor construction and
may compromise viable commercial process implementation.
Significant progress has recently been achieved regarding solar energy collectors and concentrators
while enabling to reach solar powers of several dozens of megawatts. In this context, more efficient
cycles with a lower number of steps should now be suited for operation in a broader range of
temperature from 1000 ◦ C to 2000 ◦ C. Short two-step solar-driven cycles are particularly attractive
owed to their operational simplicity favoring easier process scale implementation, thus offering the
potential for safe, low-cost, and large-scale production of H2 as a clean energy carrier [23,24]. The cycles
based on non-toxic metal oxides [25–29] using process heat at temperature above 1000 ◦ C are the
simplest and most promising routes for solar H2 production.
The solar thermochemistry governing two-step water-splitting cycles involves metal oxide redox
reactions. In the first step driven by concentrated solar energy, the reduction of the metal oxide
leads to both oxygen release and material activation. In the second water-splitting step, oxidation
of the redox-active material (reduced valence state of the metal oxide) with water steam produces
hydrogen (Figure 1). A few redox cycles have been investigated for solar hydrogen production from
water-splitting. The generic two-step process that makes use of metal oxides redox pairs is based on
the following reactions:
1
High temperature reduction step (endothermic): Mx Oy → Mx Oy−1 + O (1)
2 2
Hydrolysis step (exothermic): Mx Oy−1 + H2 O → Mx Oy + H2 (2)
Such a cycling process presents noticeable advantages: (i) the upper cycle temperature (generally
in the range of 1200–1600 ◦ C) is compatible with renewable concentrated solar energy; (ii) water and
heat are the only process inputs, hydrogen and oxygen the only chemical outputs; (iii) the produced
H2 and O2 streams are inherently separated by the different reactions; (iv) the other chemicals and
reactants are continually recycled in the closed cycle; (v) the produced H2 is pure for being directly
processed, for instance using a polymer electrolyte membrane fuel cell (PEMFC).
Conventional electrolysis, representing the state-of-the-art technology, also generates pure H2 ,
but this approach is limited by thermodynamic inefficiencies and has low overall energy conversion
efficiency as it requires first the generation of electricity (global energy conversion efficiency below
ChemEngineering 2019, 3, x FOR PEER REVIEW 3 of 28

20% when taking into account the electricity production efficiency). Thermochemical water-splitting
cycles
cycles are
are expected
expected totoreach
reachhigher
higherefficiency
efficiencythan
thanwater
waterelectrolysis
electrolysissince
sincetheir energy
their energyefficiency is
efficiency
not impaired by the intermediate conversion of heat to electricity. Benchmark
is not impaired by the intermediate conversion of heat to electricity. Benchmark is the alkalineis the alkaline water
electrolysis
water using solar
electrolysis usingelectricity generated
solar electricity by either
generated by photovoltaics (PV) or(PV)
either photovoltaics concentrating solar power
or concentrating solar
(CSP). (CSP).
power With With
currently available
currently technologies,
available technologies,thethe
overall
overallsolar-to-hydrogen
solar-to-hydrogenenergy
energy conversion
conversion
efficiency reaches 10–14%,
efficiency reaches 10–14%, when
when assuming
assuming 70%70% efficiency
efficiency forfor electrolysis
electrolysis and
and 15%
15% (PV)
(PV) to
to 20%
20% (CSP)
(CSP)
annual
annual efficiency for solar-produced electricity [30]. On the other hand, direct thermal splitting of
efficiency for solar-produced electricity [30]. On the other hand, direct thermal splitting of
water would require temperatures exceeding 2000–2500 °C
◦ to yield significant amounts
water would require temperatures exceeding 2000–2500 C to yield significant amounts of hydrogen. of hydrogen.
Therefore, thermochemical
Therefore, thermochemical cyclescycles are
are proposed
proposed to to lower
lower the maximum process
the maximum process temperature
temperature to to aa
technical manageable level.
technical manageable level.
Figure 1. Scheme of the two-step water-splitting cycle based on the Mx Oy /Mx Oy−1 system.
Figure 1: Scheme of the two-step water-splitting cycle based on the MxOy/MxOy−1 system.
The cycles working in the temperature range of 900–2000 ◦ C were not considered in previous
screening studiesworking
The cycles [10], because
in thethey were not practically
temperature compatible
range of 900–2000 °C with
werethe notoperating
considered temperature
in previous of
advanced nuclear
screening studies reactors. In contrast,
[10], because theynot
they were canpractically
be plainly considered
compatiblefor a coupling
with with concentrating
the operating temperature
of advanced nuclear reactors. In contrast, they can be plainly considered for evaluation
solar thermal as primary energy source. Therefore, a new screening, selection, and a couplingofwith the
most promising solar-driven thermochemical cycles for H production was
concentrating solar thermal as primary energy source. 2Therefore, a new screening, selection, and conducted [28]. A database
including over
evaluation 280 referenced
of the most promising thermochemical
solar-driven cycles was constructed
thermochemical at CNRS-PROMES
cycles for H2 production laboratory
was
(France) from a detailed bibliographic survey to sort out the cycles
conducted [28]. A database including over 280 referenced thermochemical cycles was constructed previously proposed in theat
literature. The developed database incorporates the detailed information
CNRS-PROMES laboratory (France) from a detailed bibliographic survey to sort out the cycles on the processing conditions,
involved chemical
previously proposed reaction steps, bibliographic
in the literature. The developed references dataincorporates
database describing or thereferring
detailedto the cycles.
information
The numerous listed cycles can be classified into a restricted number
on the processing conditions, involved chemical reaction steps, bibliographic references of defined subcategories (sulphur,
data
iodine, chlorine,
describing bromine,
or referring to carbon, miscellaneous,
the cycles. The numerous hybrid).
listedObjective
cycles canscreening criteria
be classified intowere defined
a restricted
and applied
number to decrease
of defined the number
subcategories of investigated
(sulphur, cycles to
iodine, chlorine, a manageable
bromine, carbon, number and to hybrid).
miscellaneous, identify
potentially applicable
Objective screening solar-driven
criteria cycles. and applied to decrease the number of investigated cycles
were defined
Roughly 30 interesting
to a manageable number and to identify cycles were selected
potentially forapplicable
further investigations
solar-driven by using a set of defined
cycles.
criteria:
Roughly 30 interesting cycles were selected for further investigations by using a set ofsystems,
(1) upper temperature of the cycle for being compatible with solar concentrating defined
(2) number of reactions and separation steps, (3) number of chemical elements,
criteria: (1) upper temperature of the cycle for being compatible with solar concentrating systems, (4) nature of the
(2)
cycle (either purely thermal or hybrid thermo-electrochemical), (5) thermodynamics,
number of reactions and separation steps, (3) number of chemical elements, (4) nature of the cycle (6) technical
operational
(either purelyfeasibility
thermalof or the hybrid
cycle accounting for reaction kinetics
thermo-electrochemical), (5) and chemical conversion
thermodynamics, yields,
(6) technical
(7) expectedfeasibility
operational cycle exergy of theefficiency, (8) availability
cycle accounting for reactionand cost of process
kinetics chemicals
and chemical and reactants,
conversion yields,
(9) corrosiveness, (10) presence of non-stationary solid reactants, (11) environmental
(7) expected cycle exergy efficiency, (8) availability and cost of process chemicals and reactants, safety and health (9)
issues, (12) type/availability/cost and ease for implementing the separation
corrosiveness, (10) presence of non-stationary solid reactants, (11) environmental safety and health steps. Chiefly, two and
three-step
issues, (12)cycles were retained due
type/availability/cost and to their
ease forease of processthe
implementing implementation
separation steps. andChiefly,
integrationtwo that
and
should imply favorable process economics. In addition, these cycles basically
three-step cycles were retained due to their ease of process implementation and integration that involve low number of
reactions
should and separation
imply steps (thereby
favorable process lowering
economics. penaltiesthese
In addition, associated
cycles with heat involve
basically transfer low
limitations
number andof
reactions and separation steps (thereby lowering penalties associated with heat transfer limitations
and products separation), available, low-cost, and safe (non-toxic) materials, and a heat input
temperature (900–2000 °C) compatible with concentrated solar energy.
products separation), available, low-cost, and safe (non-toxic) materials, and a heat input temperature
(900–2000 ◦ C) compatible with concentrated solar energy.
The cycles that were eliminated did not respond to the above criteria, as it was the case for those
requiring very high temperatures (higher than 2200 ◦ C) (MoO2 /Mo, SiO2 /SiO, WO3 /W), hybrid cycles
involving an electrochemical step (Cu-Cl cycle [31,32]), cycles based on toxic (Cd, Hg, or bromide) or
corrosive compounds such as potassium hydroxide, cycles that necessitate advanced gas separation
techniques (such as membrane technologies), or cycles for which thermodynamics is not favorable
such as most cycles based on sulphates [33,34] or chlorine [35–38]. In addition, a method of exergy
analysis was developed to determine the exergy requirements and the global exergy efficiency of each
selected thermochemical cycle [28]. This method was used to compare the cycles and to identify the
main operations responsible for irreversibilities, which is a thermodynamic tool for future process
optimization. Energy efficiency analyses related to process implementation in large-scale solar tower
chemical plants were conducted [29] to estimate the global solar-to-hydrogen energy conversion
efficiency that was about 20% for iron and zinc oxide cycles using currently available data (including
the different heat losses taking place in the main process sub-systems comprising solar concentrating
system for solar energy collection, solar receiver and reactor, and chemical cycling process).
The research investigations regarding high-temperature cycles were mainly focused on
CdO/Cd [39], ZnO/Zn [40–76], SnO2 /SnO [76–82], Mn2 O3 /MnO [83], CeO2 /Ce2 O3 [84–86], and
Fe3 O4 /FeO [87–95]. The utilization of mixed metal oxides (e.g. Zn-ferrite, Mn-ferrite, or Ni-ferrite
cycles [96–127]) decreases the temperature of the solar activation step (O2 release) while the reduced
oxide still remains active for the H2 generation step. Due to their promising growing interest,
increasing research activities devoted to the investigation of solar-driven two-step cycles (ZnO/Zn,
SnO2 /SnO, Mn2 O3 /MnO, Fe3 O4 /FeO, ferrites, CeO2 /CeO2−δ , perovskites) have been conducted mainly
in Switzerland (ETHZ, PSI [40]), Germany (DLR [122]), France (CNRS-PROMES [28]), USA (DOE
projects [53,54]) and Japan (Tokyo Institute of Technology [97] and Niigata University [114]).
The current studies are mainly related to thermochemical systems based on metal oxide redox
pairs as chemical intermediates. The two-step cycles commonly rely on volatile (ZnO/Zn, SnO2 /SnO)
or non-volatile redox pairs (Fe3 O4 /FeO, CeO2 /CeO2−δ , and mixed oxides). The products of the
high-temperature reduction reaction are in the gaseous state for the volatile oxide cycle category,
whereas redox reactions proceed in the condensed state for the non-volatile oxides.
2. Volatile Metal Oxide Cycles
2.1. ZnO/Zn Cycle

The ZnO/Zn cycle is classified as a volatile oxide cycle because the reduced zinc metal species
produced during the decomposition reaction (ZnO(s) → Zn(g) + 12 O2 ) is released from the reactor as a
gaseous product. This system has been studied extensively and it is considered as one of the most
attractive candidate cycles for being coupled with a solar energy source at high temperature. ZnO can
be dissociated near 1800 ◦ C in a solar reactor [58] and Zn is recovered at the reactor exit after rapid
quenching the gaseous products. The reported activation energies of the ZnO dissociation varied
in the range 312–376 kJ/mol [43,44]. The products recombination between Zn and O2 represents a
parasitic reverse reaction that limits the Zn yield from the solar step [49]. Above the Zn condensation
temperature, Zn recombination is controlled by diffusion of Zn(g) and O2 to the reactor walls [62].
The condensation of Zn vapor in the presence of O2 was studied by fractional crystallization in a
temperature-gradient tube furnace, which revealed that Zn oxidation is predominantly a heterogeneous
process and, in the absence of nucleation sites, Zn(g) and O2 can coexist in a metastable state [42].
Otherwise, quenching the products is necessary in order to avoid Zn re-oxidation, which brings
process irreversibility (energy losses) and may further introduce complexity issues during large-scale
application. The gas quenching aiming to alleviate Zn recombination issue (e.g., via the addition
of large amounts of inert gas) constitutes the main challenge of this redox cycle. A fast products
quenching to cool the gas species down to below 900 ◦ C (that corresponds to the Zn(g) condensation
temperature) is advocated [41,61]. The quenching efficiency is sensitive to the dilution ratio of Zn(g) in
a flow of inert gas [41]. Alternatively, an effective technique for in-situ Zn/O2 separation directly at high
temperatures may also be used to avoid recombination (electrothermal separation methods [128,129]).
The solar thermochemical reactor represents the main key component of solar processes involving
water-splitting cycles. A specific research effort must be thus dedicated to suitable reactor design
and optimization. The materials used for both the window and the cavity receiver must be carefully
chosen as they represent the most sensitive components of solar reactors that are commonly based
on either direct or indirect heating of the reactants using concentrated solar energy. Direct heating
provides efficient and rapid heat transfer directly to the reacting matter but such reactor technologies
must be designed so that to avoid particle deposition on the optical window (case of entrained
particles and particle-laden flow). Alternatively, indirect heating via a heat transfer wall requires
using high-temperature resistant refractory materials and may suffer from additional heat losses
due to indirect heat transfer. Conventional solar reactor designs usually make use of insulated
cavity-type blackbody receivers that allow obtaining almost isothermal conditions in the cavity volume
and high solar energy absorption efficiencies [57–61]. High-temperature resistant ceramic materials
(refractory) are usually employed for lining the inner reactor volume (including both cavity walls and
insulation materials).
Different solar reactor configurations designed for ZnO thermal dissociation have been explored
in the literature. The first simple type is based on the direct irradiation of a ZnO rod [44]. Such
a reactor involves a packed bed or a moving rod of ZnO placed behind a window at the focus of
a solar concentrating system. A number of drawbacks arise while operating such a process. First,
only the ZnO irradiated surface is solar heated, whereas the underlying ZnO remains at relatively low
temperatures, thus inducing radiative heat losses at the surface and temperature gradient through
the layer. The reactant surface area exposed to solar flux is weak when compared with a dispersed
particulate system, which results in relatively low reaction rates. High re-radiation losses also occur
because the reaction does not proceed at fast enough rate to absorb most of the incident solar energy.
This in turn reduces the process energy efficiency. Second, the necessary presence of a window requires
using a screening stream of inert gas at its surface, in order to both cool it and protect it from products
deposition. Any material or dust deposition on the window may result in opaque absorbing regions
and subsequent localized overheating and thermal stress, with a possible window melting. Another
developed reactor configuration consists of the rotating conical cavity receiver (“ROCA”). A 10 kW
prototype and 100 kW pilot were constructed and tested in a high-flux solar furnace [57–61]. The design
was based on a windowed cavity receiver that rotates at a high angular velocity. The cavity walls were
made of a refractory material (either ZrO2 , HfO2 , or ZnO itself). ZnO was fed in batch pulses by a
screw feeder, and the cavity rotation evenly dispersed the ZnO particles throughout the reactor on the
cavity walls. Incident solar radiation was absorbed through the window to heat the ZnO particles,
and products were swept by inert carrier gas into a cooling zone for rapid quenching. This reactor
concept is promising, but may face difficulties and barriers during scale-up. The limitations imposed
by the window that was protected by both water-cooling and inert gas purging, could result in a
significant decrease of process efficiency due to both conductive and convective heat losses, and energy
requirements for inert gas recycling. The cavity rotation further increases mechanical complexity to the
high-temperature chemical process, which presents significant engineering challenges and capital costs
issues upon scaling-up. Similar to other systems in which a layer of ZnO is directly heated, the lack
of particle separation, mixing, and agitation could hinder the kinetics due to heat and mass transfer
limitations. In light of the challenges to be faced by these still promising reactor prototype technologies,
the use of rapid reaction aerosol flow reactors was considered to obtain rapid ZnO decomposition
kinetics while still being scalable with existing chemical engineering technology [53–56]. The small size
of particles yields greater surface area for enhancing heat and mass transfer rates, and the increase of
this available area enhances the overall rate of surface processes. Such particles dispersed in a gas flow
have been shown to reach extremely high heating rates, on the order of 105 K s−1 , when exposed to a
nearby high temperature hot emitting surface because of their ability to efficiently absorb the radiative
heat flux from the surrounding hot walls. The increased heat and mass transfer rates in aerosol systems
fasten solid–gas reaction kinetics, lower the global residence time required for converting the particles,
and finally make such a solar receiver more efficient. Indirect solar heating of the particles stream
by infrared radiation emitted from the surrounding tube walls further eliminates the need for using
an optical window. However, low ZnO conversions were obtained (maximum 17%) and particulate
products deposition occurred on the walls [54].
The solid metallic Zn powder produced in the solar step may be used in either a fuel cell or
battery, or in the exothermal water-splitting reaction to produce pure H2 and regenerate ZnO that
can be recycled back to the solar step. The produced Zn is a solid that can be stored and fed to the
hydrolysis reactor during night time or cloudy periods. The H2 production step of the ZnO/Zn cycle
involves a surface hydrolysis reaction between solid Zn particles (or liquid molten Zn) and steam.
The Zn hydrolysis was performed and studied with steam bubbling through molten Zn at 500 ◦ C [63],
but the reaction rate and Zn conversion were limited by the formation of a ZnO(s) layer around the
steam bubbles, thus preventing efficient contact between fresh reactants. The kinetic rates of such a
surface reaction are expected to be limited by mass transfer through either the gas boundary layer or
the developing ZnO film at the surface. To maximize reaction rates during the off-sun step of the cycle,
the use of particles with a high specific surface area is beneficial, thereby reducing the resistance to
mass transfer within the particle and through the developing ZnO film.
Most of previous studies focusing on Zn particles hydrolysis reaction have been carried out either
using commercial Zn powders [71,72] or Zn produced from solar carbo-thermal ZnO reduction [73].
The Zn conversion achieved in an aerosol flow reactor fed with both water vapor and commercial Zn
particles (average particle size of 158 nm) was about 24% at 540 ◦ C with a gas residence time of about
0.6 s [67]. The reaction rate may become negligible because of a low-permeable ZnO layer growing
at the particles surface [71]. Non-isothermal thermogravimetric analysis (TGA) with Zn powder
dispersed on quartz wool showed that complete Zn conversion could be reached with longer residence
times. Regarding Zn obtained from solar carbo-thermal reduction, increasing the temperature of
injected steam flow from 200 to 550 ◦ C increased the Zn conversion from 24% to 81% during the fast
reaction stage (observed from 400 ◦ C) [73]. Besides, other studies on hydrolysis using an aerosol
flow reactor consisted of the intermediate Zn vaporization before steam quenching the Zn vapors to
co-produce both H2 and Zn/ZnO nanoparticles [64–69], but this process suffered from weak particle
yield at the outlet and significant particle deposition at the wall. The advantages of hydrolyzing
Zn nanoparticles are three-fold: (1) their high specific surface area inherently increases heat and
mass transfer, and reaction kinetics (2) their large surface-to-volume ratio favors their complete bulk
oxidation, and (3) their possible entrainment by a gas flow is suitable for allowing a simple, continuous,
and controllable feeding of Zn reactants and removal of ZnO products. The in-situ formation and
steam hydrolysis of entrained Zn nanoparticles in an aerosol (size: 70–100 nm) freshly produced
by vapo-condensation allowed reaching 70% H2 yield [64]. Ernst et al. [66] obtained up to 90% H2
yield with reactor temperatures in the range 627–1000 ◦ C, however at the expense of weak particle
yield downstream.
Finally, steam hydrolysis of Zn-rich solar-produced nanopowder (synthesized in a high
temperature solar chemical reactor) results in complete Zn particle conversion at relatively low
temperatures (360–500 ◦ C) [74]. Figure 2 shows the time course of Zn conversion during steam
hydrolysis. This conversion is obtained from the ratio between the amount of converted Zn and the
initial amount of Zn in the powder. The initial presence of ZnO clusters in the particles promotes
the Zn oxidation reaction. The complete Zn particle conversion during hydrolysis is due to both the
synthesis method and the involved mechanisms during the solar step, which allows the formation of
Zn-rich nanoparticles containing ZnO clusters dispersed in the bulk. The ZnO serves as nucleation
sites promoting further oxidation during the water-splitting step. Therefore, the solar-produced
Zn nanoparticles containing a fraction of recombined ZnO show better reaction extent than pure
Zn particles.
Figure 2. Reaction extents versus time for Zn hydrolysis during isothermal thermogravimetry at
Figure 2. Reaction extents versus time for Zn hydrolysis during isothermal thermogravimetry at
different temperatures and steam mole fractions (H2 O mole fraction of 4.4%, 7.0%, or 21%, I corresponds
different temperatures and steam mole fractions (H2O mole fraction of 4.4%, 7.0%, or 21%, I
to the time of steam injection at about 14 min) [74].
corresponds to the time of steam injection at about 14 min) [74].
Assuming an endothermic ZnO decomposition reaction performed at 2000 ◦ C,
the Assuming an endothermic
energy conversion ZnO decomposition
efficiency of ZnO/Zn reaction cycle reaches performed at 2000
about 45% °C, (equal
the energy to
conversion efficiency of ZnO/Zn cycle reaches about 45% (equal to HHV H2 / HZnO(25 °C)Zn(g)+0.5O2(2000 °C))
HHVH2 /∆HZnO(25 ◦ C)→Zn(g)+0.5O2(2000 ◦ C) ) and the maximum exergy efficiency is 29% without
and the maximum
including exergy efficiency
any heat recovery [40] (defined is 29% aswithout
the ratioincluding
of chemical anyenergy
heat recovery
stored in[40]
the(defined
form of H as the
2 at
ratio of chemical energy stored in the form of H 2 at ambient ◦ temperature
ambient temperature to the solar power input, ηexergy = −∆G H2+0.5O2→H2O /Qsolar ). Hence, the ZnO/Zn to the solar power input,
exergysystem
redox = −G°H2+0.5O2 H2O / Qsolar). Hence, the ZnO/Zn redox system presumably represents one of the
presumably represents one of the most favorable candidate cycles given its potential for
most favorable candidate
achieving both high energy and cycles given
exergy its potential
efficiencies, for achieving
although significant both high energy
technical challenges andareexergy
still
efficiencies, although significant technical challenges
remaining and the development of alternative cycles is thus necessary. are still remaining and the development of
alternative cycles is thus necessary.
2.2. SnO2 /SnO Cycle
2.2. SnO2/SnO Cycle
More recently, the new SnO2 /SnO redox pair was proposed as an efficient system for two-step
More recently,
water-splitting cyclethe
[77,78] SnO2/SnO
new which sharesredoxmanypairsimilar
was proposed as an efficient
characteristics with the system
ZnO/Zn for two-step
system,
water-splitting
including: (1) thecycle [77,78]ofwhich
formation vapor shares many similar
phase products characteristics
(volatile oxide) in thewith solarthe
step,ZnO/Zn system,
(2) the similar
including: (1)
temperature rangethe formation
required forofthermal
vapor phase products
reduction (about(volatile
1600–1800 oxide)
◦ C atinatmospheric
the solar step, (2) the (3)
pressure), similar
the
temperature range required for thermal reduction (about 1600–1800
need for dilution with neutral gas and quenching of the products in the solar step to avoid reverse°C at atmospheric pressure), (3)
the need for dilution
re-oxidation, and (4) thewith neutral gassynthesis
solar-driven and quenching of the
of reduced SnOproducts
particlesin with
the solar step to avoid
nanometric reverse
size scale by
re-oxidation, and (4) the solar-driven synthesis
vapor condensation if a fast enough quenching is applied. of reduced SnO particles with nanometric size scale
by vapor
The SnOcondensation if a fast enough quenching is applied.
2 /SnO two-step cycle thus belongs to the class of volatile metal oxide cycles, similarly to
ZnO/Zn.The The
SnOonly
2/SnOknown
two-step cycle
cycle basedthuson belongs to thewas
tin oxides class of volatilereferenced
previously metal oxide ascycles, similarly to
the “Sn-Souriau”
ZnO/Zn. The only known cycle based 1 on tin oxides was previously referenced as the ”Sn-Souriau”
three-step cycle: (i) SnO2 → SnO + 2 O2 ; (ii) 2SnO → Sn + SnO2 ; (iii) Sn + 2H2 O → SnO2 + H2 .
three-step cycle:
Nevertheless, (i) SnO2ofthis
the concept SnO cycle + ½Opatented in 1972[130]
2; (ii) 2SnO Sn +was SnO 2; (iii)
not Sn + 2H
subjected 2O 
to any SnO2 + H2.
experimental
Nevertheless, the concept of this cycle patented in 1972 [130] was not subjected
validation to confirm its operational feasibility. Recently, reaction (ii) was proven to reach completion to any experimental
atvalidation to confirm
600 ◦ C after heatingits
foroperational
10 min under feasibility.
inert gasRecently,
atmosphere reaction (ii) was
to avoid SnOproven to reach
oxidation. completion
Unfortunately,
at 600 Sn
metallic °C cannot
after heating for 10
be separated from minutes
SnO2 by under inert Sn
liquefying gasas atmosphere
advocated into theavoid
original SnO“Snoxidation.
Souriau”
Unfortunately, metallic Sn cannot be separated from SnO by liquefying
cycle, because the molten liquid phase of Sn does not form in the blend. The reaction (iii) generating
2 Sn as advocated in the
H2 from the Sn/SnO2 mixture issued from disproportionation reaction (ii) is slow and only partialThe
original “Sn Souriau” cycle, because the molten liquid phase of Sn does not form in the blend. at
reaction
600 ◦ C (Sn(iii) generating
conversion H2 from
yield of 45% theafter
Sn/SnO 2 mixture
30 min). issued
For the above from disproportionation
mentioned reasons, this reaction (ii) is
three-step
slow and only partial at 600 °C (Sn conversion yield of 45% after 30 min). For the above mentioned
reasons, this three-step cycle was not selected as a promising candidate. Instead, the following
innovative SnO2/SnO two-step cycle was proposed and assessed:
cycle was not selected as a promising candidate. Instead, the following innovative SnO2 /SnO two-step
cycle was proposed and assessed:
1
Solar reduction step: SnO2 (s) → SnO(g) + O (endothermic, 1600 ◦ C) (3)
2 2
Hydrolysis step: SnO(s) + H2 O(g) → SnO2 (s) + H2 (exothermic, 550 ◦ C) (4)
The first endothermic solid–gas reaction (∆H = 557 kJ/mol SnO2 at 1600 ◦ C) consists of the high
temperature thermal reduction of tin(IV) oxide (stannic oxide) into tin(II) oxide (stannous oxide).
The required temperature for reaction (3) is suitable for the coupling with a concentrating solar thermal
energy source. The SnO product (Tm = 1042 ◦ C, Tb = 1527 ◦ C) is gaseous at the reaction temperature,
and SnO(g) is released along with O2 . When the gas temperature drops at the reactor outlet, the gaseous
SnO vapors are condensed as nanoparticles via formation of nuclei and particle growth. As for ZnO
decomposition, this reaction is also favored by an oxygen partial pressure decrease (via vacuum
pumping or inert gas dilution) to limit the reverse recombination reaction with O2 . The beneficial effect
of high dilution ratio or reduced pressure operation was demonstrated [49]. A detailed kinetic analysis
of the recombination reaction with O2 was performed. The kinetic parameters were determined for
both SnO and Zn recombination (global reaction order of about 1.5 corresponding to the reaction
stoichiometry, and activation energies of 42 kJ/mol for SnO and 35 kJ/mol for Zn [49]).
The second solid–gas reaction generating H2 consists in hydrolyzing SnO nanoparticles by steam
water. This moderately exothermic reaction (∆H = −49 kJ/mol at 500 ◦ C) occurs above 450 ◦ C at
atmospheric pressure, with both a satisfactory SnO oxidation rate and a final H2 yield over 90%.
The recovered stannic oxide, SnO2 , is then recycled into the first reaction (solar reduction step), which
closes the cycle. The cycle H2 productivity assuming a complete reactant conversion is 166.3 mLH2 /gSnO
at normal conditions, which equates to about 14.8 mgH2 /gSnO (i.e., the H2 mass storage capacity of
SnO is 1.48 %). The potential applications of such metal oxide systems are related to the stationary or
portable generation of H2 . SnO (or Zn) can be long-term stored and transported more easily and surely
in the form of solids than H2 , which represents a potential H2 storage tank. In addition, the reduced
species are stable in air and the reactivity of SnO (or Zn) with steam water is not altered even after a
long storage period in ambient air. Therefore, on-demand H2 can be generated at the delivery site
when required.
Initially, the SnO hydrolysis was considered as an intermediate step of metallic Sn hydrolysis [131].
Subsequently, the kinetics for hydrolysis of solar-produced SnO particles (and solar Zn for
comparison), consisting of nanoparticles synthesized from solar thermal SnO2 reduction, was studied
in details [79–81]. Hydrolysis experiments were carried out to investigate the hydrolysis reaction in a
packed-bed reactor and to establish kinetic rate laws. Kinetic parameters encompassing activation
energies and reaction orders were determined (122 ± 13 kJ/mol and 2.0 ± 0.3 for SnO, and 87 ± 7 kJ/mol
and 3.5 ± 0.5 for Zn, respectively). The reduced SnO species react efficiently in the water-splitting
step to generate H2 in the range of 450–600 ◦ C. The hydrolysis reaction showed a fast initial step at
the time of steam injection before the chemical conversion gradually leveled off, which is typical for
solid–gas reactions exhibiting a passivating oxide layer growing at the particle surface. The suggested
reaction mechanism is composed of a fast reaction-controlled regime during the initial step, followed
by a diffusion-controlled regime which increasingly strengthens while the oxide layer is formed at the
particle surface. The hydrolysis of solar SnO nanoparticles nearly approached completion (Figure 3),
while Zn hydrolysis was fast and reached complete H2 yield thanks to the nano-sized powders [79].
Further thermogravimetric investigations confirmed SnO conversion approaching 90% at 600 ◦ C [80],
but competing reactions such as SnO disproportionation into Sn and SnO2 occurred concomitantly,
as evidenced by Mössbauer spectroscopy [81].
Figure 3. Evolution of chemical conversion during SnO nanoparticles hydrolysis at different

Figure 3. Evolution of chemical conversion during SnO nanoparticles hydrolysis at different temperatures.
temperatures.
Figure 3. Evolution of chemical conversion during SnO nanoparticles hydrolysis at different
The global flow diagram of the thermochemical process integrating the two chemical cycle
temperatures.
The global flow diagram of the thermochemical process integrating the two chemical cycle steps
steps (both solar reactor and hydrolyser) and the H2 utilization via fuel cell is shown in Figure 4.
(both solar reactor and hydrolyser) and the H2 utilization via fuel cell is shown in Figure 4. The
The globalHflow
The produced diagram of
is converted in the thermochemical
an ideal processboth
fuel cell generating integrating
electrical the (W = −237
two chemical
power cyclekJ/mol
steps
produced H2 is2 converted in an ideal fuel cell generating both electrical power (WFC FC = −237 kJ/mol at
at 25 ◦ C)
(both solar
andreactor
heat (QandFC =hydrolyser)
−49 kJ/mol). and The the H2 utilization
intrinsic via fuel efficiency
energy conversion cell is shown of theinSnOFigure
2 /SnO4.cycle
The
25°C) and heat (QFC = −49 kJ/mol). The intrinsic energy conversion efficiency of the SnO2/SnO cycle
produced
reaches aboutH2 is42%
converted in an
accounting forideal fuel cell
the high generating
heating value ofboth electrical
H2 (HHV =power
286 (W
kJ/mol).
FC = −237
The
H2 H2 = 286 kJ/mol). The maximum kJ/mol
maximum at
reaches about 42% accounting for the high heating value of H2 (HHV ◦
25°C) and heat (Q
solar absorption FC = −49 of
efficiency kJ/mol). The intrinsic
a perfectly insulatedenergy conversion
black-body efficiency
solar receiver of the86%
is about SnO at2/SnO
T=1600 cycleC
solar absorption efficiency of a perfectly insulated black-body solar receiver is about2 86% at T=1600
reaches about
(assuming 42% accounting
a concentration ratio = 5000
forCthe highand
heating value
a direct of H2 (HHV
normal H2 = 286
irradiation I =kJ/mol).
1 kW/mThe maximum
) 2[132]. Thus,
°C (assuming a concentration ratio C = 5000 and a direct normal irradiation I = 1 kW/m ) [132]. Thus,
solar absorption
the amount efficiency
of solar energyofinput
a perfectly
(Q insulated
) necessary black-body
to carry outsolar receiver
the is aboutSnO
endothermic 86% at T=1600
2 reduction
the amount of solar energy input solar (Qsolar) necessary to carry out the endothermic SnO 2 reduction
°C (assuming
reaction a concentration
is about 795 kJ/mol, whichratio C = 5000
then andassessing
allows a direct normal
the globalirradiation
process Iefficiencies
= 1 kW/m )of[132].
2 /SnO
SnO2Thus,
reaction is about 795 kJ/mol, which then allows assessing the global process efficiencies of SnO2/SnO
the amount
cycle. of solarglobal
The resulting energy inputprocess
exergy (Qsolar) efficiency
necessaryreaches
to carry out 29.8%
about at 1600 ◦ C, which
the endothermic SnO2 reduction
is similar
cycle. The resulting global exergy process efficiency reaches about 29.8% at 1600 °C, which is similar
◦ C. which then allows assessing the global process efficiencies of SnO2/SnO
reaction
to ZnO/Zn is about 795
cycle at kJ/mol,
2000
to ZnO/Zn cycle at 2000 °C.
cycle. The resulting global exergy process efficiency reaches about 29.8% at 1600 °C, which is similar
to ZnO/Zn cycle at 2000 °C. H SnO2(25°C)  SnO + 1/2O2(1600°C) = 684.1 kJ/mol
Qrerad QHydro = H SnO + H2O(g)  SnO2 + H2
= -55
H SnO2(25°C) kJ/mol
 SnO (at 25°C)
+ 1/2O2(1600°C) = 684.1 kJ/mol
Solar
QQ Solar W FC==H
QHydro -GSnOH2++H2O(g)
1/2O2  H2OSnO2 + H2
concentrating rerad
solar
system reactor ==-55
237kJ/mol
kJ/mol(at (at25°C)
25°C)
Solar SnO2(s)
Solar WH
FC = H2-G H2O = -286
H2O kJ/mol (at 25°C)
concentrating Qsolar + 1/2O2
H2 + 1/2O2
SnO + ½O
reactor QFC= =237 (HkJ/mol
- G) (at= -4925°C)kJ/mol (at 25°C)
system 2
SnO2(s) HH2 + 1/2O2 H2O HSnO2= -286
 SnOkJ/mol
 1/2O2 (at 
25°C)
4
  1 T 86% (T = 1600°C)
SnO + ½O2 QFCabsorption
= (H - G) = Q -49 kJ/mol (at 25°C)
solar I.C
HSnO2 4
WFC Filter Qsolar= 795.1
absorption kJ/mol
 SnO  1/2O2
1T 86% (T = 1600°C)
SnO(s)
Qrerad= 111 kJ/mol Qsolar I.C
QFC Filter Qsolar= 795.1 kJ/mol
WFC Cycle energy efficiency:
SnO(s)
Qrerad= 111 kJ/mol
QFC ½O2 ΔH H2  1/2O2  H2O
η cycleenergy
  41 .8%
Fuel Cell Hydrolyser QHydroCycle efficiency:
ΔH SnO2  SnO  1/2O2
½O2 ΔHefficiencies:
H2 O η Process

cycle
H2  1/2O2  H2O
 41 .8%
Fuel Cell Hydrolyser QHydro ΔH SnO2
WFC SnO  1/2O2
H2
H2 O
η exergy 
Process  29 .8 %
efficiencies:
Q solar
WFC
H2 η exergy   ΔH
ηenergy  29
H2 .8 % H2O 35 .9 %
 1/2O2
Q solar Q
solar
ΔH H2  1/2O2  H2O
ηenergy  35 .9 %
Figure 4. Block diagram of the process and energy efficiency Q solar of the two-step SnO2 /SnO
analysis
Figure 4. Block diagram of the process and energy efficiency analysis of the two-step SnO2/SnO
thermochemical cycle.
Figure 4. Block diagram of the process and energy efficiency analysis of the two-step SnO2/SnO
A lab-scalesolar
A lab-scale solar reactor
reactor prototype
prototype (Figure
(Figure 5) was5)designed,
was designed,
operated,operated, and for
and simulated simulated for
application
application to the solar
to the solar thermal thermal
reduction reduction
of volatile of volatile
metal metal oxides
oxides involved in theinvolved
first step in
of the first step of
thermochemical
thermochemical
cycles. This reactor features a windowed rotating cavity receiver, in which dispersed soliddispersed
cycles. This reactor features a windowed rotating cavity receiver, in which reacting
solid reacting
particles particles are injected
are continuously continuously injectedsystem
by a feeding by a feeding
[46,47].system [46,47].generated
The volatile The volatile generated
products are
products
subsequently are subsequently
recovered at the recovered
outlet asat the outlet asagglomerates
nanoparticles nanoparticlesinagglomerates
a downstreaminceramic
a downstream
filter for
ceramic filter forhydrolysis
the subsequent the subsequent
step. Thehydrolysis step. The
oxide particles oxideand
injected particles injected
dispersed and
in the dispersed in the
directly-irradiated
directly-irradiated
cavity under a controlledcavityinert
under a controlled
atmosphere serveinert atmosphere as
simultaneously serve
bothsimultaneously
reacting speciesasinboth reacting
the solid–gas
species in the solid–gas decomposition reaction and as radiative absorbers
decomposition reaction and as radiative absorbers enabling homogeneous heating. The direct particles enabling homogeneous
heating.
irradiationThe direct particles
provides efficient irradiation
and rapid heatprovides
transferefficient
to the and rapid
reaction heat
site, transfer
thus to thethe
bypassing reaction site,
limitations
thus bypassing
imposed the limitations
by indirect transfer imposed by indirect transfer
of high-temperature heat via of high-temperature
intermediate absorbing heat viaopaque
intermediate
walls.
absorbing opaque walls. The solar ZnO dissociation was successfully performed
The solar ZnO dissociation was successfully performed as a function of the cavity pressure and as a function of the
cavity pressure
inert carrier gasand inert carrier
flow-rate, and thegas obtained
flow-rate,Zn andproduct
the obtained
yield inZntheproduct yieldpowder
collected in the collected
reached
powder
above 90%. reached above 90%.
The reaction extent The
(ZnOreaction extent was
conversion) (ZnO conversion)
highly dependent wasonhighly dependent
the particle on the
temperature
particle temperature and the particle conversion increased markedly when
and the particle conversion increased markedly when the particle temperature slightly increased. the particle temperature
slightly
Likewise, increased. Likewise,
the conversion the conversion
increased increased
when decreasing thewhen
initialdecreasing
diameter ofthe fedinitial diameter
particles of fed
according to
particles according to computational fluid dynamics (CFD) simulations of the
computational fluid dynamics (CFD) simulations of the reactive gas-particle flow. As a result, complete reactive gas-particle
flow. As was
reaction a result, complete
predicted when reaction was predicted
the particles temperature whenexceeds
the particles
1927 ◦ C temperature exceedsdiameter
for initial particle 1927 °C
for µm. particle diameter of 1 m.
of 1initial
Figure 5. Rotating cavity-type solar reactor designed for continuous volatile metal oxide processing.
Figure 5: Rotating cavity-type solar reactor designed for continuous volatile metal oxide processing.
Another optimised solar reactor, shown in Figure 6, was then designed enabling the
continuous
Another measurement
optimised solarand reactor,
monitoringshownof several operating
in Figure parameters
6, was then designed (evolution
enablingofthe temperatures,
continuous
O2 concentration
measurement andat monitoring
the reactor outlet, Figureoperating
of several 7), and theparameters
synthesis of(evolution
significantof amounts of solar Zn
temperatures, O2
and SnO nanopowders (active materials) for the exothermal hydrolysis step [48].
concentration at the reactor outlet, Figure 7), and the synthesis of significant amounts of solar Zn and Scanning electron
microscopy
SnO (SEM) characterizations
nanopowders (active materials) (Figure 8) show
for the that these
exothermal powders are
hydrolysis stepcomposed of agglomerates
[48]. Scanning electron
of nanoparticles
microscopy (10–50
(SEM) nm) with a high specific
characterizations (Figuresurface
8) showarea (20–60 m2 /g).powders
that these This vertical-axis cavity-type
are composed of
solar reactor (1 kW of thermal power absorbed) effects the reaction above 1600 ◦ C at2reduced pressure
agglomerates of nanoparticles (10–50 nm) with a high specific surface area (20–60 m /g). This vertical-
(about
axis 20 kPa) with
cavity-type solarthe compressed
reactor (1 kW ofoxide
thermal reactant
powerinjected
absorbed) at effects
the cavity base by above
the reaction the means
1600 of
°Can at
ascending
reduced screw piston.
pressure (about 20 This
kPa)reactor wascompressed
with the also used to determine
oxide the
reactant kinetics
injected at of
thethe ZnObase
cavity andbySnOthe2
dissociation
means reactions by
of an ascending fitting
screw reaction
piston. This models withalso
reactor was experimental data [50]
used to determine the thanks
kineticsto of
anthe
inverse
ZnO
method
and SnOinvolving the reactions
2 dissociation online diagnosis
by fitting ofreaction
outlet gas combined
models with with a reactordata
experimental model [50]coupling
thanks toheat
an
and mass transport phenomena, radiation, and chemical reaction. The activation
inverse method involving the online diagnosis of outlet gas combined with a reactor model coupling energy of the oxide
dissociation
heat and mass reaction was phenomena,
transport determined to be 313 ± and
radiation, 31 kJ/mol
chemicalfor ZnO
reaction. The±activation
and 353 18 kJ/mol energy
for SnOof2 [50].
the
oxide dissociation reaction was determined to be 313 ± 31 kJ/mol for ZnO and 353 ± 18 kJ/mol for
SnO2 [50].
ChemEngineering2019,
ChemEngineering 2019,3,3,63x FOR PEER REVIEW 1111ofof2828
Figure 6. Solar reactor with continuous injection of compressed rod of oxide reactant (ZnO or SnO2)
Figure
for 6. Solar reactor
nanopowder with
synthesis (Zncontinuous injection of compressed rod of oxide reactant (ZnO or SnO2)
or SnO). injection
Figure Solar
6. 6.
Figure Solarreactor
reactorwith
with continuous
continuous compressedrod
injection of compressed rodofofoxide
oxidereactant
reactant (ZnO
(ZnO oror
SnOSnO
2) 2 )
for nanopowder synthesis (Zn or SnO).
forfor
nanopowder
nanopowder synthesis
synthesis(Zn
(ZnororSnO).
SnO).
Figure 7. Evolution of temperatures and outlet O2 concentration measurements in the solar reactor
Figure 7. Evolutionofoftemperatures
temperaturesandand outlet
outlet O
O2 concentration measurements inin
the solar reactor
Figure
Figure7.
during 7.Evolution
ZnO Evolution of temperatures
dissociation (shutter fully and outlet
opened at 2 2concentration
O
time concentration
zeroand
measurements
andclosedmeasurements
closed after2150
2150s)s) inthe
thesolar
[48]. solarreactor
reactor
during
during ZnO dissociation (shutter fully opened at time zero after [48].
duringZnO
ZnOdissociation
dissociation(shutter
(shutterfully
fullyopened
openedatattime
timezero
zeroand
andclosed
closedafter
after2150
2150s)s)[48].
[48].
Figure 8. SEM images solar-produced

of solar-produced powders of SnO
(A) SnO (B)
andZn
(B)synthesized
Zn synthesized from thermal
solar
Figure 8.8. SEM
Figure SEMimages
imagesofof powders
solar-produced of (A)
powders of (A) and
SnO and from solar
(B) Zn synthesized from solar
thermal
reduction reduction of corresponding oxides followed by gas quenching.
thermal 8.ofSEM
corresponding
Figure reduction images of oxides
of corresponding followed
solar-produced by gas quenching.
powders
oxides followed of gas
by (A)quenching.
SnO and (B) Zn synthesized from solar
thermal reduction of corresponding oxides followed by gas quenching.
3. 3. Non-Volatile
Non-Volatile MetalOxide
Metal OxideCycles
Cycles
3. Non-Volatile Metal Oxide Cycles
3. Non-Volatile Metal Oxide
The iron oxide-based O4 /FeO) two-step cycle is particularly attractive because it features
(Fe3Cycles
simple reactants and chemical steps (in comparison with nuclear-based cycles) and available safe
ChemEngineering2019,
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28
The iron oxide-based (Fe3O4/FeO) two-step cycle is particularly attractive because it features
reactants (resulting
simple reactants andinchemical
lower irreversibility inducing with
steps (in comparison potentially superiorcycles)
nuclear-based cycle energy efficiency).
and available safe
Furthermore, it also involves non-corrosive solid materials involved in solid–gas reactions,
reactants (resulting in lower irreversibility inducing potentially superior cycle energy efficiency). and it
avoids the drawback
Furthermore, of potential
it also involves reverse recombination
non-corrosive solid materials reaction
involvedwithin O 2 duringreactions,
solid–gas gas quenching
and it
commonly encountered with volatile metal oxides such as zinc, tin or cadmium
avoids the drawback of potential reverse recombination reaction with O2 during gas quenching oxides [62,88]. A key
benefit relies on the fact that non-volatile iron oxide systems proceed with the continuous
commonly encountered with volatile metal oxides such as zinc, tin or cadmium oxides [62,88]. A key release and
removal of theon
benefit relies evolved
the factgaseous O2 from the
that non-volatile condensed
iron reacting
oxide systems phase with
proceed during thethe solar reduction
continuous releasestep,
and
thus promoting high reduction extents. The
removal of the evolved gaseous O2 from the condensed Fe O
3 4 /FeO redox pair was originally proposed
reacting phase during the solar reduction by
Nakamura [87]. This two-step
step, thus promoting cycle proceeds
high reduction extents. as
Thefollows:
Fe3O4/FeO redox pair was originally proposed by
Nakamura [87]. This two-step cycle proceeds as follows:
Solar reduction step: Fe3 O4 (l-s) → 3FeO(l-s) + 1/2O2 (5)
Solar reduction step: Fe3O4(l-s)  3FeO(l-s) + 1/2O2 (5)
Hydrolysis step: 3FeO(s) + H2 O(g) → Fe3 O4 (s) + H2 (6)
Hydrolysis step: 3FeO(s) + H2O(g)  Fe3O4(s) + H2 (6)
The ◦=
The first
firsthigh-temperature
high-temperaturesolar solarstepstep(thermal
(thermalreduction
reductionofofFeFe 3O3O4 )4)isishighly
highlyendothermic
endothermic(∆H (H°=
319.5
319.5 kJ/mol),
kJ/mol),whereas
whereas thethe
second
second low-temperature
low-temperature step step
(FeO (FeO
hydrolysis) is slightly
hydrolysis) exothermic
is slightly (∆H◦ =
exothermic
−33.6
(H°=kJ/mol). The amount
−33.6 kJ/mol). The of solar energy
amount of solartheoretically needed to produce
energy theoretically needed1 to molproduce
of H2 corresponds
1 mol of H to2
the summation of the sensible energy required to heat 1 mol of Fe O from 600 ◦ C to 2100 ◦ C (446.51 kJ),
corresponds to the summation of the sensible energy required 3to 4heat 1 mol of Fe3O4 from 600 °C to
the
2100endothermic
°C (446.51 kJ), reduction enthalpy (242.84
the endothermic reductionkJ),enthalpy
and the energy
(242.84required
kJ), and the to heat andrequired
energy vaporizeto water
heat
from 25 ◦ C to 600 ◦ C (64.9 kJ) [126]. On the basis of these temperature levels and the HHV of H
and vaporize water from 25°C to 600 °C (64.9 kJ) [126]. On the basis of these temperature levels and 2
(286 kJ/mol), the theoretical energy conversion efficiency
the HHV of H2 (286 kJ/mol), the theoretical energy conversion3 efficiency of Fe O 4 /FeO cycle is 37.1%.
of Fe3O4/FeO cycle is 37.1%.
The
The high-temperature solar thermal reduction of magnetite to wüstite theoretically
high-temperature solar thermal reduction of magnetite to wüstite theoretically proceeds
proceeds at at
temperatures above 2200 ◦ C under 1 bar (according to Gibbs free energy variation) [133]. In addition
temperatures above 2200 °C under 1 bar (according to Gibbs free energy variation) [133]. In addition
to
to stoichiometric
stoichiometric FeO, FeO, thermodynamics
thermodynamics predicts predicts thethe formation
formation of of non-stoichiometric
non-stoichiometric wüstite wüstite phases
phases
(Fe
(Fe1−y O such as Fe0.947O)
1−yO such as Fe0.947
O)(Figure
(Figure 9). 9). The
The thermal
thermal reduction
reduction of of magnetite
magnetite has has been
been experimentally
experimentally
studied [88–94] and
studied [88–94] anddemonstrated
demonstratedby byusing
usinga 2a kW
2 kW (thermal
(thermal power)
power) parabolic
parabolic solarsolar concentrator.
concentrator. The
The reduction of magnetite was only noticeable at temperatures above
reduction of magnetite was only noticeable at temperatures above the Fe3O4 melting point (1597 °C). the Fe 3 O4 melting point
(1597 ◦
TofighiC). Tofighi
et al. [89,90] et showed
al. [89,90]
thatshowed
a 0.8 g that
samplea 0.8 g sample
reached 80%reached
conversion 80%afterconversion
5 min atafter
20005°Cmin at
in an
2000 ◦ C in an Ar atmosphere (the conversion in air only reaches 40%). Because of the high temperature
Ar atmosphere (the conversion in air only reaches 40%). Because of the high temperature thermal
thermal
treatment, treatment,
the Fe3O4the Fe3 O4 reduction
reduction occurs concomitantly
occurs concomitantly with a slight with a slight
material material vaporization.
vaporization. Weidenkaff
Weidenkaff
et al. [92] reported that the exothermic hydrolysis reaction of wüstite with steamwith
et al. [92] reported that the exothermic hydrolysis reaction of wüstite water steam water is
is influenced
influenced by the non-stoichiometry, structure and morphology of the
by the non-stoichiometry, structure and morphology of the parent wüstite phases and by the reaction parent wüstite phases and by
the reaction temperature.
temperature. The water-splitting
The water-splitting hydrolysis
hydrolysis reaction using reaction using FeOonly
FeO is favorable is favorable
below 800 only
°C below
(when
800 ◦ C (when ∆G◦ < 0) and the theoretical FeO conversion decreases with increasing temperature
G°<0) and the theoretical FeO conversion decreases with increasing temperature according to
according
thermodynamicsto thermodynamics
(Figure 10). (Figure 10).
Figure 9. Thermodynamic equilibrium composition of the Fe-O system (1 mol of Fe2 O3 , 100 mol of N2 ,
Figure 9. Thermodynamic equilibrium composition of the Fe-O system (1 mol of Fe2O3, 100 mol of N2,
P = 1 bar).
P = 1 bar).
ChemEngineering 2019,3,3,63
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Figure 10. Thermodynamic equilibrium composition of the Fe-O-H system (3 mol of FeO, 1 mol of
H2O, N2 atmosphere, P = 1 bar).
H2 O, N2 atmosphere, P = 1 bar).
H 2O, N2 atmosphere,
Besides, P = thermal
the complete 1 bar). reduction of hematite (Fe2O3) into wüstite was achieved in a high-
temperature solar
Besides, the reactor thermal
complete operatedreduction
at 1600 °C of and 0.1 bar
hematite (Feunder inert gas atmosphere [93]. The
2 O3 ) into wüstite was achieved in a
Besides, the
oxygen-releasing complete
reaction thermal
proceeds reduction
via the of hematite
formation
◦
high-temperature solar reactor operated at 1600 C and 0.1 bar under (Fe
of 2O3molten
the ) into wüstite
inertwas
oxide gasachieved
and in about
itatmosphere
requires a high-
[93].2
temperature
minutes
The solar reactor
to reach completion,
oxygen-releasing operated at 1600
which confirms
reaction proceeds °C and
via thepreviously 0.1 bar under
formation reported inert
results.
of the molten gas atmosphere
Further
oxide and TGA [93]. The
experiments
it requires about
2oxygen-releasing
confirmed
min to reach reaction
thatcompletion,
wüstite proceeds
formation via near
starts
which confirms thepreviously
formation of the molten
the Fe3O4 reported
melting point
results.oxide
(Figure and
11).itTGA
Further Therequires
reducedabout 2
oxide
experiments
minutes to reach
is thus recovered
confirmed
completion,
as aformation
that wüstite
which
hardened starts confirms
structure
nearthat
previously
the Fe cannot reported results. Further TGA experiments
react with water efficiently and the milling of
3 O4 melting point (Figure 11). The reduced oxide is
confirmed
the that wüstite
solar-reduced materialformation
into a starts
fine near the
powder is Fe3O
then 4 meltingto
necessary point
carry (Figure
out the11). The reduced
subsequent oxide
hydrolysis
thus recovered as a hardened structure that cannot react with water efficiently and the milling of the
is thus recovered as a hardened structure that cannot react with water efficiently and the milling of
step.
solar-reduced material into a fine powder is then necessary to carry out the subsequent hydrolysis step.
the solar-reduced material into a fine powder is then necessary to carry out the subsequent hydrolysis
step. 0 0
1 -0,5
-5
0 Fe 2O 3 - Fe 3O4 0
Thermal reduction -1
-10 1 -0,5
-5 Fe 2O 3 - Fe 3O4
2
-1,5
/uVFlow /uV
TG (mg) TG (mg)
Thermal reduction -1
-15
-10
2 Fe 3O4 -2
3 -1,5
-20
Heat
-15 Towards FeO

Heat Flow
Fe 3O4 -2,5
-2
4
-25 3
-20 -3
Towards FeO
-2,5
4
-30
-25 -3,5
Mel ting Fe3 O4 -3
-35 -4
-30 -3,5
0 500 1000
Mel ting Fe3 O4 1500 2000
-35 T (° C) -4
0 500 1000 1500 2000
Figure 11. Thermogravimetric analysis TGA (mass loss signal in mg) and differential thermal analysis
T (° C)
Figure
DTA 11.flow
(heat Thermogravimetric analysis
signal in microvolt) of FeTGA (mass loss signal in mg) and differential thermal analysis
2 O3 under Ar atmosphere.
DTA (heat flow signal in microvolt) of Fe2O3 under Ar atmosphere.
Figure
A 11. Thermogravimetric
quantitative gas analysis analysis TGA (mass
of the amount of Hloss signal in mg)
2 evolved wasand differential
performed inthermal analysisway
a continuous
DTA (heat
to determine flow
A quantitative signal
the reaction in microvolt)
gas analysis
kineticsofandof Fe O
the chemical
amount of
2 3 under Ar atmosphere.
H2 evolvedofwas
conversion performed
wüstite in a continuous
hydrolysis. wayofto
A conversion
determine
83% the reaction
was measured kinetics
regarding theand chemicalreaction
hydrolysis conversion
at 575 of◦wüstite hydrolysis. A conversion
C of non-stoichiometric of 83%
solar-produced
was A quantitative
measured gas
regardinganalysis
the of the
hydrolysis amount of
reactionH evolved
2at 575 °C was
of performed in a
non-stoichiometric
wüstite (Fe(1−y) O) milled into a fine powder (particle size of 30–50 µm) [93]. The hydrolysis kinetics is continuous way
solar-produced to
determine
wüstite (Feon
dependent the the
(1−y) reaction
O)oxide
milled kinetics and
into a fine
material chemical
powder
physical conversion
(particlereaction
properties, of wüstite
size of 30–50 hydrolysis.
m) [93].
temperature, andThe A conversion
hydrolysis
particle of 83%
kinetics
size (Figure 12).is
was
The measured
dependent
reaction on regarding
ratethedecreases the hydrolysis
oxide material
with physical
time becausereaction
properties,at reaction
575 °C of
of the formation of anon-stoichiometric
temperature, solar-produced
and particle
low permeable oxide size(Fe
layer (Figure
3 4)
O
wüstite
12). The (Fe (1−y)O) milled
reaction rate into a
decreases fine powder
with time (particle
because size
of theof 30–50
formationm) [93].
of a The
low
at the particles surface, which then grows with time and hinders the reaction. The hydrolysis reaction hydrolysis
permeable kinetics
oxide is
layer
dependent
of(Fe on
3O4) at the
particles the oxide material
particles surface,
is governed by two which physical properties,
then controlling
successive reaction
grows with phenomena: temperature,
time and hinders and particle
the reaction.
the fast size (Figure
The hydrolysis
steam oxidation of the
12). The surface
reaction
external reaction
of particlesofrateisdecreases
governed
particle with
followed time
by two
by because
successive
steam of the inside
formation
controlling
diffusion of a lowthe
phenomena:
the particle permeable
fast The
pores. steamoxide layer
oxidation
maximum
(Fe 3O4) at the particles surface, which then grows with time and hinders the reaction. The hydrolysis
initial hydrolysis reaction rates were achieved for solar-produced wüstite, enabling a bulk hydrogen
reaction of particles is governed by two successive controlling phenomena: the fast steam oxidation
ChemEngineering
of the external2019, 3, 63 of particle followed by steam diffusion inside the particle pores. The maximum
surface 14 of 28
initial hydrolysis reaction rates were achieved for solar-produced wüstite, enabling a bulk hydrogen
production
production at at the
the beginning
beginning of of the
the reaction
reaction with steam corresponding
with steam corresponding to to the
the rapid
rapid oxidation
oxidation of of the
the
surface area. The higher reaction rates obtained with solar FeO-rich powders are due
surface area. The higher reaction rates obtained with solar FeO-rich powders are due to the formation of to the formation
of non-stoichiometric wüstite phases (Fe O with  close to 0.05) during the solar synthesis step.
non-stoichiometric wüstite phases (Fe1−δ O1−with δ close to 0.05) during the solar synthesis step. Indeed,
Indeed,
solar thermal processing of materials is commonlyischaracterized
solar thermal processing of materials commonly characterized
by high heating byandhigh heating rates
quenching and
quenching rates favoring formation of defects and cation vacancies in the lattice
favoring formation of defects and cation vacancies in the lattice structure, in turn yielding materialsstructure, in turn
yielding
with high materials
contentswith high contents of non-stoichiometric
of non-stoichiometric phases, as validatedphases,by as validated by thermodynamics
thermodynamics predicting the
predicting the formation of different non-stoichiometric wüstite
formation of different non-stoichiometric wüstite phases at high temperature. phases at high temperature.
In summary, In
wüstite
summary, wüstite hydrolysis is hindered by the formation of a Fe 3O4 diffusion barrier and the use of
hydrolysis is hindered by the formation of a Fe3 O4 diffusion barrier and the use of fine particles,
fine particles,
obtained obtained
for instance for instance
from from anmechanical
an intermediate intermediate mechanical
particle grindingparticle grinding
step, is needed step, is needed
to improve the
to improve the particle conversion extent. In contrast, the two-step iron oxide
particle conversion extent. In contrast, the two-step iron oxide cycle (Fe3 O4 /FeO) involves low3O cycle (Fe 4/FeO)
cost and
involves
abundantlow cost and
chemical abundantand
compounds chemical compoundsbecome
could potentially and could potentially
an attractive become
option an attractive
for large-scale H2
option for large-scale H 2 production in future solar processes, thus requiring the design,
production in future solar processes, thus requiring the design, demonstration and scale-up of efficient
demonstration
and reliable solar and scale-up
reactor of efficient and reliable solar reactor technologies.
technologies.
Figure 12. Evolution of chemical conversion rates during continuous FeO hydrolysis producing H2 as
Figure 12: Evolution
a function of chemical
of the temperature conversion
(FeO rates during continuous FeO hydrolysis producing H2 as
c : commercial FeO, FeOs : solar-produced FeO) [93].
a function of the temperature (FeOc: commercial FeO, FeOs: solar-produced FeO) [93]
Regarding other metal-oxide redox systems, most of them are not feasible practically because
they Regarding
require a too other
much metal-oxide redox systems,
elevated temperature during most of them
the solar are notstep
reduction feasible < 0 for T > because
(∆G◦ practically 2200 ◦ C
in the case of MoO2 /Mo, SnO2 /Sn, TiO2 /TiO2−x , MgO/Mg, or CaO/Ca redox pairs). In contrast,
they require a too much elevated temperature during the solar reduction step (G°<0 for T>2200 °C
in
thethe case of MoO
non-volatile 2/Mo, SnO
systems such2/Sn,as TiO
Co32O 4 /CoO
/TiO 2−x, MgO/Mg,
and Mn3 Oor 4 /MnO
CaO/Ca redoxredox pairs).
pairs In contrast,
exhibit the non-
a low reduction
volatile systems ◦
such as Co O ◦/CoO and Mn O /MnO redox pairs exhibit
temperature (902 C and 1537 C in air, respectively), but the hydrolysis step is not thermodynamically
3 4 3 4 a low reduction temperature
(902 °C and
feasible 1537 °C in air,
(thermodynamic respectively),
calculations but H
predict the hydrolysis
2 yields belowstep 1% foris not thermodynamically
two-step cycles involving feasible
these
(thermodynamic
oxides [35,133]). calculations predict H2 yields below 1% for two-step cycles involving these oxides
[35,133]).
In order to lower the maximum temperature of the solar reduction step, ferrite cycles
wereInalternatively
order to lower the maximum
proposed [97,98]. temperature
Oxygen deficient of thewith solarcation
reduction
excess step,
Ni-Mnferrite cycles
spinel were
ferrites
alternatively
(Ni0.5 Mn0.5 Fe2proposed
O4−δ with δ[97,98].
indicating Oxygen
the oxygendeficient with of
deficiency cation excesswere
the spinel) Ni-Mn
proven spinel ferrites
to be capable
(Ni
for 0.5 Mn0.5
both Fe2O4− with  below
water-splitting indicating800 ◦the oxygen
C and deficiency
regeneration of the spinel)
(oxygen release)wereabove 800 ◦ C
proven to[98].
be capable
However,for
both
the low water-splitting
water-splitting below 800 °Cof
capability and
theregeneration
(Ni,Mn)-ferrite (oxygen
system release) abovefrom
was arising 800 °C [98].
their However,
small contentthein
low water-splitting capability of the (Ni,Mn)-ferrite system was arising
activated oxygen deficiency (oxygen vacancies) reached in the solid [96]. Strategies for improving the from their small content in
activated
amount ofoxygenoxygendeficiency
vacancies(oxygen
in solid vacancies)
compounds reached
have thus in thebeensolid [96]. Strategies for improving the
investigated.
amount Theof oxygen
partial vacanciesofiniron
substitution solid
by compounds have thus been
nickel [115], manganese [95], investigated.
cobalt [114], aluminum-copper [113]
or zincThe partial substitution
[103–111] of ironstructure
in the Fe3 O4 spinel by nickelforms [115],mixed
manganese
iron oxides[95],ofcobalt
general[114], aluminum-copper
formula (Fe1−x Mx )3 O4 .
[113] or zinccan
This ferrite [103–111]
be reducedin theatFe 3O4 spinel
much lowerstructure
temperaturesformsthan mixed ironrequired
those oxides of forgeneral
Fe3 O4 formula
thermal
(Fe 1−xMx)3O
reduction 4. This
(thus ferrite can
avoiding be reduced
melting), while theat much
reduced lower
phase temperatures
(Fe1−x Mx )1−y than
O isthose requiredtofor
still capable Fe3O4
perform
water-splitting [95]. Allendorf et al. [127] reported detailed thermodynamic analysis applied to ferrites
(MFe2 O4 , with M = Co, Ni, or Zn). Their results point out that the use of ferrites is beneficial because
the thermal reduction step is thermodynamically more favorable in comparison with pure iron oxide
(Fe3 O4 ). Thermodynamics also indicates that Ni-ferrite shows the most favorable combination of both
thermal reduction and hydrolysis reaction.
Among many feasible cycles, the Zn/Fe3 O4 system was able to react with H2 O to form H2 and
ZnFe2 O4 (Zn-ferrite) at 600 ◦ C [103,104]. Nevertheless, to form metallic Zn during the O2 -releasing
step, either lowering the O2 partial pressure or cooling the gas mixture was necessary to avoid metallic
Zn oxidation, as for the ZnO/Zn cycle [110]. It was further shown that the H2 production reaction can
be carried out by using both ZnO and Fe3 O4 to split water, which is thus more attractive since the
O2 -releasing step does not require any quenching step and can simply proceed in air at 1500 ◦ C [105].
3 ZnO + 2 Fe3 O4 + H2 O → 3 ZnFe2 O4 + H2 T = 600–8000 ◦ C (7)
1
3 ZnFe2 O4 → 3 ZnO + 2 Fe3 O4 + O T = 1500 ◦ C (8)
2 2
As previously observed for the Fe3 O4 /FeO system, mixed iron oxides may similarly undergo rapid
deactivation during thermochemical cycling due to coarsening and sintering of the iron oxide particles.
The use of refractory ceramics as stable supports can help to alleviate material sintering, and enhance
H2 productivity without deactivation through cyclic reaction. Hence, the ferrite particles were
supported on monoclinic ZrO2 fine particles (m-ZrO2 ) that provide a good resistance to agglomeration
(densification) and sintering at the working temperatures of 1000–1400 ◦ C, because m-ZrO2 features a
higher melting point than ferrite while being chemically inert to ferrite material at high temperatures.
As a result, repeatable and stable thermochemical performance during two-step water-splitting cycles
was demonstrated by using active ZrO2 -supported ferrite particles [114–117].
In addition, partially-stabilized tetragonal zirconia (t-PSZ) and yttria-stabilized cubic zirconia
(c-YSZ) can also be used as an inert support [112,118]. Thermochemical cycling involving Fe-YSZ
particles is suitable to alleviate the iron oxides sintering or melting at high temperatures thanks to the
incorporation of active Fe ions into the YSZ crystal lattice, thus resulting in enhanced and reproducible
thermochemical performance of the cyclic reaction. The suggested mechanism was based on the fact
that the YSZ support can react with particles of ferrite at temperatures above 1400 ◦ C in an inert
atmosphere, in turn forming a solid solution. For Fe3 O4 /c-YSZ (ZrO2 doped with over 8 mol% of
Y2 O3 ), the following mechanism was proposed [118]:
(1) Formation of Fe2+ -YSZ at 1400 ◦ C (under N2 ):
x/3Fe3 O4 + Yy Zr1−y O2−y/2 → Fe2+ x Yy Zr1−y O2−y/2+x + x/6O2 (9)
(2) Water-splitting at 1000 ◦ C (60 min.) and thermal reduction at 1400 ◦ C (30 min.):
Fe2+ x Yy Zr1−y O2−y/2+x + x/2H2 O → Fe3+ x Yy Zr1−y O2−y/2+3x/2 + x/2H2 (10)
Fe3+ x Yy Zr1−y O2−y/2+3x/2 → Fe2+ x Yy Zr1−y O2−y/2+x + x/4O2 (11)
In parallel to the fundamental research on the abovementioned redox working materials,

a number of solar chemical reactor concepts have been designed and developed. These include
reactors incorporating multi-channel honeycomb structures [122–124] and ceramic foams coated with
ferrite [117,118], rotary-type reactors [120,126], and fluidized beds [119].
Further advances on ferrite-based systems have been proposed in the collaborative EU-project
HYDROSOL (coordinated by APTL/CERTH from Greece) aiming to operate the complete redox cycle
in a single solar receiver/reactor [124]. This reactor features multi-channeled ceramic (siliconized
and recrystallized SiC) honeycomb structures coated with active redox materials (iron oxide-based)
capable for both water-splitting at 800 ◦ C and regeneration at 1300 ◦ C (temperature-swing cycle).
This operational technique using a fixed reactant integrated inside the reactor avoids the need of
continuous particle feeding and collection at the process outlet (no solid flow). The monolithic
ceramic structure acts as an efficient volumetric solar absorber. The whole cycling process can be
achieved in a single solar energy receiver/converter and it approaches a configuration similar to that
encountered in automobile exhaust catalytic converters. The water steam flowing inside the ceramic
structure oxidizes the reduced activated material producing pure hydrogen. Then, the material must
be reduced during the regeneration step by increasing the solar receiver temperature, allowing a
cyclical operation in a single reactor. Various compositions of M-Zn-doped iron oxides (M=Mn or
Ni) with a spinel or wüstite phase structure were synthesized via aerosol spray pyrolysis (ASP) and
combustion self-propagating high-temperature synthesis (SHS) [124,125], and then used as coatings on
the monolith [122]. A pilot-scale (100 kW) solar reactor equipped with two parallel ceramic monolithic
supports operating in opposite modes was then developed for quasi-continuous H2 production [123].
The favored redox systems are zinc- and nickel/zinc-based ferrites. The reaction scheme in the case of
zinc can be written as follows:
ZnFe2+ y Fe3+ 2−y O4−y/2 + xH2 O → ZnFe2+ y−x/2 Fe3+ 2−y+x/2 O4−y/2+x + xH2 (12)
ZnFe2+ y−x/2 Fe3+ 2−y+x/2 O4−y/2+x → ZnFe2+ y Fe3+ 2−y O4−y/2 + x/2O2 (13)
Gokon et al. [117,118] proposed and tested ceramic foam materials made of MgO-partially
stabilized Zirconia (MPSZ). The porous foam was coated with both c-YSZ and Fe3 O4 particles
(Fe3 O4 /YSZ/MPSZ foam device) and it effectively absorbs solar radiation due to the large specific
surface area. The H2 generation from Fe3 O4 /YSZ/MPSZ foam devices is associated with the redox
transition of Fe2+ -Fe3+ ions in the YSZ lattice. The deactivation of Fe3 O4 due to high-temperature
sintering can be alleviated because the active Fe2+ ions remain in the YSZ lattice. The same ceramic
foams were used with coatings made of NiFe2 O4 /m-ZrO2 powders that exhibit the highest reactivity
among the ferrite/zirconia systems.
Diver et al. [126] developed a concept of counter-rotating ring receiver/reactor/recuperator (CR5)
enabling efficient sensible heat recovery during cyclic reactions to reach acceptable thermal efficiencies.
The solar-driven heat engine is composed of a stack of counter-rotating rings to which are attached fins
made of an active metal oxide ceramic. While the rings rotate, the metal oxide material moves alternately
through a high temperature solar reduction zone and a lower temperature water-splitting zone. Since
the fins counter-rotate, sensible heat can be internally recovered, thus reducing the overall energy
input requirements for the aim of improving efficiencies.
Kaneko et al. [120] also developed a similar concept of rotary-type solar reactor integrating Ni-Mn
ferrite loaded on a YSZ support.
Gokon et al. [119] proposed and tested a solar reactor for two-step water-splitting using m-ZrO2
supported NiFe2 O4 particles processed in an internally circulating fluidized bed. The ferrite particle
conversion of approximately 45% was reached upon 1 kW of input simulated power supplied by
Xe-beam irradiation. The proposed solar reactor concept was considered to be suited for being
associated with beam-down optics [134].
Finally, the two-step cycle based on cerium oxides (CeO2 /Ce2 O3 ) was first demonstrated in
2006 by Abanades and Flamant [84], consisting of two chemical steps: (1) solar reduction, 2CeO2 →
Ce2 O3 + 1/2O2 ; (2) hydrolysis, Ce2 O3 + H2 O → 2CeO2 + H2 . CeO2 was first reduced into Ce2 O3
during material melting over 2000 ◦ C under inert atmosphere at reduced pressure (10–20 kPa),
which induced also a partial sublimation of CeO2 . The reduced material was pounded into powder
(50–150 µm) for the hydrolysis tests. Then, an efficient reaction of Ce2 O3 with water producing H2 was
observed with a rapid and complete oxidation of Ce(III) oxide below 500 ◦ C. The high reactivity of
Ce2 O3 with steam (3 mmolH2 /gCe2 O3 ) was shown to be the main interest of the CeO2 /Ce2 O3 cycle.
This observation opened the door to a new research area related to the mixed oxide cycles containing
cerium oxides [135,136]. Similar to ferrite cycles, the targeted result is the significant decrease of the
reduction temperature of Ce(IV) into Ce(III) species, while taking advantage of the high reactivity
of Ce(III) species with water (and/or CO2 ). Early studies on ceria-based materials synthesis and
physicochemical
ChemEngineering 2019, characterization
3, x FOR PEER REVIEW at CNRS-PROMES laboratory (France) showed that binary systems 17 of 28
such as CeO2 -ZrO2 solid solutions can be promising candidates for two-step water-splitting.
The
Thethermodynamic
thermodynamicand andkinetic
kineticproperties
propertiesof ofceria
ceriacan canbe bealtered
alteredby bydoping
dopingits its fluorite
fluorite structure
structure
with transition metals and rare earth metal oxides [135–154].
with transition metals and rare earth metal oxides [135–154]. Indeed, ceria is an active compound Indeed, ceria is an active compound used
in many
used in catalytic systems,
many catalytic and it isand
systems, attractive due to itsdue
it is attractive thermal
to itsstability
thermal(good stabilityresistance to sintering)
(good resistance to
and abilityand
sintering) to exchange
ability tooxygen exchange via oxygen
storing via andstoring
releasing and oxygen
releasingreversibly.
oxygen This oxygenThis
reversibly. mobility
oxygen is
mainly
mobility restricted
is mainly to restricted
the material to surface
the materialunlesssurface
the ceria is modified
unless the ceria byisadding
modified another oxide, such
by adding anotheras
typically
oxide, such zirconia, whichzirconia,
as typically favors the material
which favors bulkthereduction
material bulk thanks to enhanced
reduction thanks oxygen diffusion
to enhanced rates.
oxygen
However, oxidation
diffusion rates. thermodynamics
However, of Zr-substitutedof
oxidation thermodynamics systems are not assystems
Zr-substituted favorable areas not foraspure ceria.
favorable
The
as foraddition of dopants
pure ceria. in ceria fluorite
The addition of dopants structure
in ceria(Mx Ce 1−x O2 ,structure
fluorite where the(M added
xCe1−xmetal
O2, whereM is commonly
the added
ametal
trivalent
M iscation like Y3+a, trivalent
commonly La3+ , Gd3+ , Sm3+
cation , PrY
like 3+
La3+3+,or
3+,, Sc Gd tetravalent
3+, Sm3+, Pr cation
3+, Sc3+ like
or Zr 4+ or Hf4+ ) shows a
tetravalent cation like
favorable
Zr4+ or Hfimpact
4+) shows onathe thermodynamics
favorable impact on of theceria reduction, andofthis
thermodynamics ceriaapproach
reduction, hasandbeen extensively
this approach
investigated for improving
has been extensively the ionicfor
investigated conductivity
improvingof the solid
ionic oxide fuel cells,of
conductivity which
solidisoxide
directly
fuellinked to the
cells, which
extent of oxygen
is directly linkedvacancies.
to the extent The addition
of oxygen of dopants
vacancies. hasThe been shown to
addition of enhance
dopantsthe hasreduction
been shown extent to
at low oxygen
enhance partial pressure
the reduction extent at when
low compared
oxygen partial withpressure
un-doped ceriacompared
when (at the expense however of
with un-doped lower
ceria (at
oxidation
the expense capability
however with of water). Hence, thecapability
lower oxidation introduction withofwater).
dopantsHence,
such asthe Zrintroduction
[145–154], Smof[139] and
dopants
transition
such as Zr metals oxides Sm
[145–154], (MO[139]
x withand M =transition
Mn, Ni, Fe, Cu) [135,140,141]
metals oxides (MOhas x withbeenMextensively
= Mn, Ni,explored Fe, Cu)
for applications
[135,140,141] hasinbeensolar-driven
extensively thermochemical redox cycles,inassolar-driven
explored for applications an efficient means to enhance
thermochemical the
redox
thermodynamic
cycles, as an efficient driving force meansof to theenhance
O2 -releasing the reduction
thermodynamic reactiondriving
at lowerforce temperatures.
of the O2However,
-releasing
itreduction
should bereaction
noted that trivalent
at lower dopants do However,
temperatures. not improve significantly
it should the thermochemical
be noted that trivalent dopants performance
do not
of ceria because
improve they dothe
significantly not thermochemical
present any meaningful performance increase ofofceria
the fuel production
because they do or improvement
not present any of
the thermal stability.
meaningful increase of the fuel production or improvement of the thermal stability.
The
Thedeviation
deviationfrom fromoxygenoxygenstoichiometry
stoichiometry(δ(ininCeO CeO 2−), otherwise known
2−δ known as as the
the oxygen
oxygen storage
storage
capacity,
capacity,isisdirectly
directly related to the
related to maximum
the maximum amount of H2 capable
amount of being of
of H2 capable generated during oxidation.
being generated during
While the oxygen exchange capability of ceria is lower compared
oxidation. While the oxygen exchange capability of ceria is lower compared to iron oxide-based to iron oxide-based cycles, sintering
iscycles,
less problematic
sintering isbecause the meltingbecause
less problematic point isthe considerably
melting point higher. Different research
is considerably higher. works have
Different
evidenced
research works the high havepromise of ceriathe
evidenced forhigh
application
promise to of
solarceriafuelforproduction
application according
to solartofuelthe redox cycle
production
represented
according toin the Figure
redox 13, using
cycle various
represented ceria inmicrostructures
Figure 13, using and various
morphologies including dispersed
ceria microstructures and
powders
morphologies [140–149], three-dimensionally
including dispersed powders ordered macroporous
[140–149], (3DOM) powders
three-dimensionally featuring
ordered templated
macroporous
macro-scale
(3DOM) powders porosity [154,155],
featuring porous structured
templated macro-scale monoliths
porosity[137–139],
[154,155],porousporousfelts or fibers monoliths
structured [156,157],
or reticulated
[137–139], porous
porous feltsfoams [158–160].
or fibers The morphologies
[156,157], or reticulated enabling porous foams both enhanced
[158–160].available geometric
The morphologies
surface
enabling area
both andenhanced
bulk interconnected pore system
available geometric surface that area
facilitate the mass
and bulk transport ofpore
interconnected reacting
system species
that
to and from the oxidation sites, are the most suitable for rapid fuel
facilitate the mass transport of reacting species to and from the oxidation sites, are the most suitable production. Optimized materials
shaping
for rapidis fuelthus production.
required to provide Optimized a good solar absorptivity
materials shaping is thus favoring homogeneous
required to provideheating,a goodalong solar
with a high specific
absorptivity favoring surface area favoring
homogeneous heating,solid–gas
along with reactions.
a highAspecific
long-term thermal
surface area stability
favoringissolid–also
required for theAconsidered
gas reactions. long-term ceria thermalstructures
stability regardless
is also requiredof the involved
for the shaping
considered method.ceria However,
structures
the materialofshaping
regardless the involved process represents
shaping method.an additional
However,step the required
material for the preparation
shaping of tailored
process represents an
materials
additionaland stepforrequired
their incorporation in suitable
for the preparation ofsolar reactors,
tailored whichand
materials could for have
theiran impact on the
incorporation in
process
suitableeconomics.
solar reactors, which could have an impact on the process economics
Figure 13. Cycles based on nonstoichiometric oxides (substituted ceria) for syngas production.
Figure 13. Cycles based on nonstoichiometric oxides (substituted ceria) for syngas production.
The amount of O2 released during the reduction step (oxygen non-stoichiometry, δ) at 1400 ◦ C
The
and the amount of
associated O2 released
reduction yieldduring
dependthe reduction step
significantly (oxygen
on the and amount of Zr)introduced
non-stoichiometry,
presence at 1400 °C
and the associated reduction yield depend significantly on the presence and amount of Zr introduced
in the materials [149]. The reduction yields of the materials (Ce3+/Cetotal) range from 6% for pure un-
doped ceria to 28% for 50%-Zr in Zr-substituted ceria during the first cycle. By increasing the Zr
amount in ceria, the reduction yield increases linearly. This result points out the beneficial effect of
Zr addition in promoting Ce4+ reduction (Figure 14). In contrast, the presence of trivalent dopants has
no noticeable effect on the material reducibility and hydrogen production yield.
Given that Zr4+ cation is not reducible, the gravimetric amount of O2 released per unit mass of
material (thus the potential H2 production) evolves differently compared to the ceria reduction yield.
The materials
ChemEngineering with
2019, 3, 63 Zr content over 25% are the most suitable compounds in term of 18 oxygen
of 28
availability and mobility. The Figure 15 represents the evolution of the O2 amount released from the
ceria materials during the reduction step as a function of the Zr content. In contrast to the evolution
inofthe
thematerials
reduction[149].
yieldThe reduction
(Figure yields
14), the of the materials
gravimetric amount of (CeO2 /Ce
3+
total ) range
released tends from 6% for
to reach pure
a plateau
Zr additionceria
un-doped in promoting
to 28% forCe 4+ reduction (Figure 14). In contrast, the presence of trivalent dopants has
50%-Zr in Zr-substituted ceria during the first cycle. By increasing the Zra
above roughly 25% of Zr content. The quantity of oxygen released reaches a threshold because
no noticeable
amount effect on the material reducibility and hydrogen production yield.
balanceinsettles:
ceria, the
the reduction
reduction yield
yield increases
is indeed linearly.
increasedThis resultthe
whereas points out the
number beneficial cation
of reducible effect of
(CeZr4+)
Given
addition in that Zr4+ cation
promoting Ce 4+ is not reducible,
reduction (Figure the
14).gravimetric
In contrast, amount
the of O2ofreleased
presence trivalentper unit mass
dopants has of
no
in ceria/zirconia solid solution is concomitantly decreased when increasing the Zr content.
material (thus
noticeable effectthe
onpotential H2 production)
the material reducibilityevolves differently
and hydrogen compared
production to the ceria reduction yield.
yield.
The materials with Zr content over 25% are the most suitable compounds in term of oxygen
availability and mobility. The Figure 15 represents the evolution of the O2 amount released from the
ceria materials during the reduction step as a function of the Zr content. In contrast to the evolution
of the reduction yield (Figure 14), the gravimetric amount of O2 released tends to reach a plateau
above roughly 25% of Zr content. The quantity of oxygen released reaches a threshold because a
balance settles: the reduction yield is indeed increased whereas the number of reducible cation (Ce4+)
in ceria/zirconia solid solution is concomitantly decreased when increasing the Zr content.
Figure 14. Evolution of the measured reduction yield in ceria-based materials at 1400 ◦ C in Ar as a
function of the
Figure 14. Zr content
Evolution [149].
of the measured reduction yield in ceria-based materials at 1400 °C in Ar as a
function of the Zr content [149].
Given that Zr4+ cation is not reducible, the gravimetric amount of O2 released per unit mass of
material (thus the potential H2 production) evolves differently compared to the ceria reduction yield.
The materials with Zr content over 25% are the most suitable compounds in term of oxygen availability
and mobility. The Figure 15 represents the evolution of the O2 amount released from the ceria materials
during the reduction step as a function of the Zr content. In contrast to the evolution of the reduction
yield (Figure 14), the gravimetric amount of O2 released tends to reach a plateau above roughly 25% of
Figure The
Zr content. 14. Evolution
quantity of oxygen
the measured reduction
released reachesyield in ceria-based
a threshold materials
because at 1400
a balance °C in
settles: Arreduction
the as a
yield function ofincreased
is indeed the Zr content 4+
[149].the number of reducible cation (Ce ) in ceria/zirconia solid solution
whereas
is concomitantly decreased when increasing the Zr content.
Figure 15. Evolution of the measured amount of oxygen released during the reduction step at 1400 °C
in Ar as a function of the Zr content [149].
The steam hydrolysis of the Zr-substituted ceria powders was also studied as a function of the
reaction temperature (850 °C, 950 °C, and 1050 °C) for 25%-Zr content and a reduction temperature
Figure 15. Evolution of the measured amount of oxygen released during the reduction step at 1400 ◦ C
Figure
in Ar as15. Evolution
a function of of
thethe
Zrmeasured amount of oxygen released during the reduction step at 1400 °C
content [149].
in Ar as a function of the Zr content [149].
reaction temperature (850 °C, 950 °C, and 1050 °C) for 25%-Zr content and a reduction temperature

reaction temperature (850 ◦ C, 950 ◦ C, and 1050 ◦ C) for 25%-Zr content and a reduction temperature in
in the previous step of 1400 °C. The H2/O2 ratio increases with temperature and equals two at 1050
the previous step of 1400 ◦ C. The H2 /O2 ratio increases with temperature and equals two at 1050 ◦ C
°C with a final amount of H2 produced of 240 µmol/g (Figure 16). The kinetic parameters based on
with a final amount of H2 produced of 240 µmol/g (Figure 16). The kinetic parameters based on
Arrhenius law have been identified from these isothermal experiments and the obtained activation
Arrhenius law have been identified from these isothermal experiments and the obtained activation
energy was found to be 51 kJ/mol for the hydrolysis reaction [145].
energy was found to be 51 kJ/mol for the hydrolysis reaction [145].
Figure 16. Production of hydrogen at different temperatures during steam hydrolysis of Zr-substituted
Figure 16. Production of hydrogen at different temperatures during steam hydrolysis of Zr-
ceria (25%-Zr) [145].
substituted ceria (25%-Zr) [145].
More recently, perovskites of the form ABO3−δ have emerged as a new attractive class of
More recently, perovskites of the form ABO3− have emerged as a new attractive class of
nonstoichiometric oxides that are widely unexplored for thermochemical cycles [161–173]. These
nonstoichiometric oxides that are widely unexplored for thermochemical cycles [161–173]. These
oxygen-deficient materials exhibit interesting characteristics concerning oxygen storage capacities and
oxygen-deficient materials exhibit interesting characteristics concerning oxygen storage capacities
transport properties through oxygen vacancies formation. Dopants can be substituted on both A and
and transport properties through oxygen vacancies formation. Dopants can be substituted on both A
B cation sites, and thus the number of potential material configurations is substantially greater than
and B cation sites, and thus the number of potential material configurations is substantially greater
for ceria-based systems. Elevated water-splitting activity has been demonstrated in La1−x Srx MnO3−δ
than for ceria-based systems. Elevated water-splitting activity has been demonstrated in
materials, so-called LSM (lanthanum strontium manganite) perovskites (Figure 17) [166], and
La1−xSrxMnO3−δ materials, so-called LSM (lanthanum strontium manganite) perovskites (Figure 17)
H2 fuel production performance comparing favorably to that of CeO2 has been evidenced in
[166], and H2 fuel production performance comparing favorably to that of CeO2 has been evidenced
Sr- and Mn-substituted LaAlO3 [173], with H2 productions (up to around 300 µmol/g with
in Sr- and Mn-substituted LaAlO3 [173], with H2 productions (up to around 300 µmol/g with
Srx La1−x Mny Al1−y O3−δ for one cycle with thermal reduction at 1350 ◦ C and oxidation at 1000 ◦ C) that
SrxLa1−xMnyAl1−yO3− for one cycle with thermal reduction at 1350 °C and oxidation at 1000 °C) that
are only slightly lower than those measured for Zr-substituted ceria. The controlled introduction of Sr
are only slightly lower than those measured for Zr-substituted ceria. The controlled introduction of
into LaMnO3 allows for tuning the redox thermodynamics in the La1−x Srx MnO3 compositional series.
Sr into LaMnO3 allows for tuning the redox thermodynamics in the La1−xSrxMnO3 compositional
Decreasing the amount of substituted Sr in LSM enhanced the re-oxidation yield at the expense of a
series. Decreasing the amount of substituted Sr in LSM enhanced the re-oxidation yield at the expense
lowered final reduction extent (lower δ), thus decreasing the global amount of generated H2 . The rate of
of a lowered final reduction extent (lower ), thus decreasing the global amount of generated H2. The
hydrogen production decreased when increasing Sr content, confirming that the intermediate materials
rate of hydrogen production decreased when increasing Sr content, confirming that the intermediate
formulations offer the most favorable combination of redox properties with trade-off between reduction
materials formulations offer the most favorable combination of redox properties with trade-off
and oxidation thermodynamics. The observed evolution of the Mn oxidation state during cycles in
between reduction and oxidation thermodynamics. The observed evolution of the Mn oxidation state
manganite perovskites implied that partial re-oxidation of Mn3+ into Mn4+ occurred, thus highlighting
during cycles in manganite perovskites implied that partial re-oxidation of Mn3+ into Mn4+ occurred,
the activation of Mn4+ /Mn3+ redox pair in the perovskites (whereas it is not active in Mn2 O3 /Mn3 O4 ).
thus highlighting the activation of Mn4+/Mn3+ redox pair in the perovskites (whereas it is not active in
Based on the possible number of doping schemes, series of even more attractive materials certainly
Mn2O3/Mn3O4). Based on the possible number of doping schemes, series of even more attractive
remain to be discovered.
materials certainly remain to be discovered.
Summary of
Figure 17. Summary of the
the hydrogen
hydrogen produced
produced after
after the
the first and second water-splitting
water-splitting step and
determined from
determined from TG analysis
analysis for different perovskite compounds as function of temperatures of
reduction/re-oxidation.
4. Conclusions
4. Conclusions
The hydrogen production from water-splitting using solar-driven thermochemical redox cycles
The hydrogen production from water-splitting using solar-driven thermochemical redox cycles
based on metal oxide reactions is an attractive route for sustainable and carbon-neutral solar fuel
based on metal oxide reactions is an attractive route for sustainable and carbon-neutral solar fuel
generation. Such cycles involve endothermic reactions that make use of concentrated solar radiation as
generation. Such cycles involve endothermic reactions that make use of concentrated solar radiation
external heat source for supplying high-temperature process energy. Thermochemical water-splitting
as external heat source for supplying high-temperature process energy. Thermochemical water-
processes efficiently convert concentrated solar energy into storable and transportable clean fuels.
splitting processes efficiently convert concentrated solar energy into storable and transportable clean
Concentrating high-flux solar technologies including solar towers and parabolic dishes are already
fuels. Concentrating high-flux solar technologies including solar towers and parabolic dishes are
applied at large-scale for commercial electricity and power generation. They may be further coupled
already applied at large-scale for commercial electricity and power generation. They may be further
to chemical reactors for solar fuel production with potential solar-to-fuel energy conversion efficiencies
coupled to chemical reactors for solar fuel production with potential solar-to-fuel energy conversion
exceeding 20–25%. Therefore, thermochemical redox cycles should represent an attractive pathway for
efficiencies exceeding 20–25%. Therefore, thermochemical redox cycles should represent an attractive
solar fuels production at competitive costs while further outperforming benchmark water electrolysis
pathway for solar fuels production at competitive costs while further outperforming benchmark
process using solar electricity generated by photovoltaics (PV) or concentrating solar power (CSP).
water electrolysis process using solar electricity generated by photovoltaics (PV) or concentrating
In contrast to the direct thermolysis of H2 O above 2500 ◦ C, thermochemical water-splitting
solar power (CSP).
cycles proceed at lower maximum operating temperatures and produce both H2 and O2 in separate
In contrast to the direct thermolysis of H2O above 2500 °C, thermochemical water-splitting cycles
steps, thereby avoiding their recombination and bypassing the need for high-temperature and
proceed at lower maximum operating temperatures and produce both H2 and O2 in separate steps,
costly downstream gas separation. Promising systems under investigation include two-step cycles
thereby avoiding their recombination and bypassing the need for high-temperature and costly
based on metal oxide redox pairs. The feasibility of solar chemical reactor technologies for the
downstream gas separation. Promising systems under investigation include two-step cycles based
thermal dissociation of volatile oxides (ZnO, SnO2 ) was demonstrated and the necessity to operate at
on metal oxide redox pairs. The feasibility of solar chemical reactor technologies for the thermal
reduced pressure under low oxygen partial pressure or to implement gas quenching was especially
dissociation of volatile oxides (ZnO, SnO2) was demonstrated and the necessity to operate at reduced
highlighted to avoid recombination between reduced species and oxygen, and to reach significant
pressure under low oxygen partial pressure or to implement gas quenching was especially
oxide conversions. Non-volatile metal oxides cycles (Fe O4 /FeO, CeO2 /Ce2 O3 , Ce- and Fe-based mixed
highlighted to avoid recombination between reduced3 species and oxygen, and to reach significant
oxides, and perovskites) can be operated with continuous removal/separation of the evolved O2 from
oxide conversions. Non-volatile metal oxides cycles (Fe3O4/FeO, CeO2/Ce2O3, Ce- and Fe-based mixed
the condensed reduced phase during the solar reduction step, so that high reduction extents/rates
oxides, and perovskites) can be operated with continuous removal/separation of the evolved O2 from
may be expected without requiring any quenching step. The reduction step proceeds with the
the condensed reduced phase during the solar reduction step, so that high reduction extents/rates
material remaining in the condensed state and the evolved O2 can be released and swept by a flow
may be expected without requiring any quenching step. The reduction step proceeds with the
of inert gas, thus avoiding recombination issues. Non-stoichiometric oxides (CeO2−δ , ABO3−δ ) have
material remaining in the condensed state and the evolved O2 can be released and swept by a flow of
been considered for decreasing the temperature of the reduction step below 1400 ◦ C, in turn alleviating
inert gas, thus avoiding recombination issues. Non-stoichiometric oxides (CeO2−, ABO3−) have been
material sintering and implying enhanced performance stability and cyclability. In contrast to the zinc
considered for decreasing the temperature of the reduction step below 1400 °C, in turn alleviating
and tin-based systems, ceria and perovskites remain in the solid state with their crystalline structure
material sintering and implying enhanced performance stability and cyclability. In contrast to the
maintained stable throughout. Identification of materials formulations with improved redox activity,
zinc and tin-based systems, ceria and perovskites remain in the solid state with their crystalline
high oxygen transport and exchange properties, and long-term stability over extended cyclic operation
structure maintained stable throughout. Identification of materials formulations with improved
under concentrated solar irradiation is required, as well as their relevant shaping as 3D porous
redox activity, high oxygen transport and exchange properties, and long-term stability over extended
structures capable to absorb concentrated solar radiation while offering large available geometrical
cyclic operation under concentrated solar irradiation is required, as well as their relevant shaping as
surface area for the solid/gas reactions. Such materials can be integrated in monolithic solar reactors
3D porous structures capable to absorb concentrated solar radiation while offering large available
geometrical surface area for the solid/gas reactions. Such materials can be integrated in monolithic
with enhanced efficiency and scalability for future application, in which O2 and H2 are produced by
temperature-swing cyclic operation through sequential reduction and oxidation steps. Development
of solar reactors incorporating heat recuperation between the reduction and oxidation steps is also
challenging to help improving the overall energy conversion efficiency. The current scientific and
technical challenges for developing clean and efficient H2 production processes based on innovative
two-step cycles are thus related to various research areas involving materials science and chemistry,
solar reactors and process engineering.
Funding: This research was partly funded by French National Research Agency (ANR, grant number
ANR-09-JCJC-0004-01 and ANR-16-CE06-0010).
Conflicts of Interest: The authors declare no conflict of interest. The funders had no role in the design of the
study; in the collection, analyses, or interpretation of data; in the writing of the manuscript, or in the decision to
publish the results.
References
1. Yadav, D.; Banerjee, R. A review of solar thermochemical processes. Renew. Sustain. Energy Rev. 2016, 54,
497–532. [CrossRef]
2. Yilmaz, F.; Tolga Balta, M.; Selbaş, R. A review of solar based hydrogen production methods. Renew. Sustain.
Energy Rev. 2016, 56, 171–178. [CrossRef]
3. Villafán-Vidales, H.I.; Arancibia-Bulnes, C.A.; Riveros-Rosas, D.; Romero-Paredes, H.; Estrada, C.A.
An overview of the solar thermochemical processes for hydrogen and syngas production: Reactors,
and facilities. Renew. Sustain. Energy Rev. 2017, 75, 894–908. [CrossRef]
4. Agrafiotis, C.; Roeb, M.; Sattler, C. A review on solar thermal syngas production via redox pair-based
water/carbon dioxide splitting thermochemical cycles. Renew. Sustain. Energy Rev. 2015, 42, 254–285.
[CrossRef]
5. Beghi, G.E. A decade of research on thermochemical hydrogen at the Joint Research Centre, Ispra. Int. J.
Hydrogen Energy 1986, 11, 761–771. [CrossRef]
6. Funk, J.E. Thermochemical hydrogen production: Past and present. Int. J. Hydrogen Energy 2001, 16, 185–190.
[CrossRef]
7. Yalcin, S. A review of nuclear hydrogen production. Int. J. Hydrogen Energy 1989, 14, 551–561. [CrossRef]
8. Bamberger, C.E.; Richardson, D.M. Hydrogen production from water by thermochemical cycles. Cryogenics
1976, 16, 197–208. [CrossRef]
9. Bamberger, C.E. Hydrogen production from water by thermochemical cycles; A 1977 update. Cryogenics
1978, 18, 170–183. [CrossRef]
10. Brown, L.C.; Besenbruch, G.E.; Lentsch, R.D.; Schultz, K.R.; Funk, J.F.; Pickard, P.S.; Marshall, A.C.;
Showalter, S.K. High Efficiency Generation of Hydrogen Fuels Using Nuclear Power; GA-A24285; General Atomics:
San Diego, CA, USA, December 2003.
11. Kameyama, H.; Yoshida, K. Reactor design for the UT-3 thermochemical hydrogen production process. Int. J.
12. Kameyama, H.; Tomino, Y.; Sato, T.; Amir, R.; Orihara, A.; Aihara, M.; Yoshida, K. Process simulation of
‘MASCOT’ plant using the UT-3 thermochemical cycle for hydrogen production. Int. J. Hydrogen Energy
1989, 14, 323–330. [CrossRef]
13. O’Keefe, D.; Allen, C.; Besenbruch, G.; Brown, L.; Norman, J.; Sharp, R.; McCorkle, K. Preliminary results
from bench-scale testing of a sulfur-iodine thermochemical water-splitting cycle. Int. J. Hydrogen Energy
1982, 7, 381–392. [CrossRef]
14. Oztürk, I.T.; Hammache, A.; Bilgen, E. An improved process for H2 SO4 decomposition step of the sulfur-iodine
cycle. Energy Convers. Mgmt. 1995, 36, 11–21. [CrossRef]
15. Kubo, S.; Nakajima, H.; Kasahara, S.; Higashi, S.; Masaki, T.; Abe, H.; Onuki, K. A demonstration study on a
close-cycle hydrogen production by the thermochemical water-splitting iodine-sulfur process. Nucl. Eng.
Design 2004, 233, 347–354. [CrossRef]
16. Kubo, S.; Kasahara, S.; Okuda, H.; Terada, A.; Tanaka, N.; Inaba, Y.; Ohashi, H.; Inagaki, Y.; Onuki, K.; Hino, R.
A pilot test plan of the water-splitting iodine-sulfur process. Nucl. Eng. Design 2004, 233, 355–362. [CrossRef]
17. Noglik, A.; Roeb, M.; Rzepczyk, T.; Hinkley, J.; Sattler, C.; Pitz-Paal, R. Solar Thermochemical Generation of
Hydrogen: Development of a Receiver Reactor for the Decomposition of Sulfuric Acid. J. Sol. Energy Eng.
2009, 131, 011003. [CrossRef]
18. Kolb, G.J.; Diver, R.B.; Siegel, N. Central-Station Solar Hydrogen Power Plant. J. Sol. Energy Eng. 2007, 129,
19. Bilgen, C.; Broggi, A.; Bilgen, E. The solar Cristina process for hydrogen production. Sol. Energy 1986, 36,
20. Sakurai, M.; Bilgen, E.; Tsutsumi, A.; Yoshida, K. Adiabatic UT-3 thermochemical process for hydrogen
production. Int. J. Hydrogen Energy 1996, 21, 865–870. [CrossRef]
21. Sakurai, M.; Miyake, N.; Tsutsumi, A.; Yoshida, K. Analysis of a reaction mechanism in the UT-3
thermochemical hydrogen production cycle. Int. J. Hydrogen Energy 1996, 21, 871–875. [CrossRef]
22. Sakurai, M.; Bilgen, E.; Tsutsumi, A.; Yoshida, K. Solar UT-3 thermochemical cycle for hydrogen production.
Sol. Energy 1996, 57, 51–58. [CrossRef]
23. Graf, D.; Monnerie, N.; Roeb, M.; Schmitz, M.; Sattler, C. Economic comparison of solar hydrogen generation
by means of thermochemical cycles and electrolysis. Int. J. Hydrogen Energy 2008, 33, 4511–4519. [CrossRef]
24. Pregger, T.; Graf, D.; Krewitt, W.; Sattler, C.; Roeb, M.; Möller, S. Prospects of solar thermal hydrogen
production processes. Int. J. Hydrogen Energy 2009, 34, 4256–4267. [CrossRef]
25. Bilgen, E.; Bilgen, C. Solar hydrogen production using two-step thermochemical cycles. Int. J. Hydrogen
Energy 1982, 7, 637–644. [CrossRef]
26. Steinfeld, A.; Kuhn, P.; Reller, A.; Palumbo, R.; Murray, J.; Tamaura, Y. Solar-processed metals as clean energy
carriers and water-splitters. Int. J. Hydrogen Energy 1998, 23, 767–774. [CrossRef]
27. Abanades, S. Hydrogen production technologies from solar thermal energy. Green 2011, 1, 209–220. [CrossRef]
28. Abanades, S.; Charvin, P.; Flamant, G.; Neveu, P. Screening of water-splitting thermochemical cycles
potentially attractive for hydrogen production by concentrated solar energy. Energy 2006, 31, 2805–2822.
[CrossRef]
29. Charvin, P.; Abanades, S.; Lemort, F.; Flamant, G. Analysis of solar processes for hydrogen production from
water-splitting thermochemical cycles. Energy Convers. Manag. 2008, 49, 1547–1556. [CrossRef]
30. Romero, M.; Buck, R.; Pacheco, J.E. An update on solar central receiver systems, projects, and technologies.
J. Sol. Energy Eng. 2002, 124, 98–108. [CrossRef]
31. Dokiya, M.; Kotera, Y. Hybrid cycle with electrolysis using Cu-Cl system. Int. J. Hydrogen Energy 1976, 1,
32. Wentorf, R.H.; Hanneman, R.E. Thermochemical hydrogen generation. Science 1974, 185, 311–319. [CrossRef]
[PubMed]
33. Ducarroir, M.; Tmar, M.; Bernard, C. Possibilités de stockage de l’énergie solaire à partir de sulfates.
Revue Phys. Appl. 1980, 15, 513–528. [CrossRef]
34. Kameyama, H.; Yoshida, K.; Kunii, D. A method for screening possible thermochemical decomposition
processes for water using ∆G0 -T diagrams. Chem. Eng. J. 1976, 11, 223–229. [CrossRef]
35. Lundberg, M. Model calculations on some feasible two-step water splitting processes. Int. J. Hydrogen Energy
1993, 18, 369–376. [CrossRef]
36. Knoche, K.F.; Cremer, H.; Steinborn, G.; Schneider, W. Feasibility studies of chemical reactions for
thermochemical water splitting cycles of the iron-chlorine, iron-sulfur and manganese-sulfur families.
Int. J. Hydrogen Energy 1977, 2, 269–289. [CrossRef]
37. Knoche, K.F.; Schuster, P. Thermochemical production of hydrogen by a vanadium/chlorine cycle. Part 1:
An energy and exergy analysis of the process. Int. J. Hydrogen Energy 1984, 9, 457–472. [CrossRef]
38. Knoche, K.F.; Cremer, H.; Steinborn, G. A thermochemical process for hydrogen production. Int. J. Hydrogen
Energy 1976, 1, 23–32. [CrossRef]
39. Ambriz, J.J.; Sibieude, F.; Ducarroir, M. Preparation of cadmium by thermal dissociation of CdO using solar
energy. Int. J. Hydrogen Energy 1982, 7, 143–153. [CrossRef]
40. Steinfeld, A. Solar hydrogen production via a two-step water-splitting thermochemical cycle based on
Zn/ZnO redox reactions. Int. J. Hydrogen Energy 2002, 27, 611–619. [CrossRef]
41. Palumbo, R.; Ledé, J.; Boutin, O.; Elorza Ricart, E.; Steinfeld, A.; Muller, S.; Weidenkaff, A.; Fletcher, E.A.;
Bielicki, J. The production of Zn from ZnO in a high-temperature solar decomposition quench process.
I—The Scientific framework for the process. Chem. Eng. Sci. 1998, 53, 2503–2517. [CrossRef]
42. Weidenkaff, A.; Steinfeld, A.; Wokaun, A.; Auer, P.O.; Eichler, B.; Reller, A. Direct solar thermal dissociation
of zinc oxide: Condensation and crystallization of zinc in the presence of oxygen. Sol. Energy 1999, 65, 59–69.
[CrossRef]
43. Weidenkaff, A.; Reller, A.W.; Wokaun, A.; Steinfeld, A. Thermogravimetric analysis of the ZnO/Zn water
splitting cycle. Thermochimica Acta 2000, 359, 69–75. [CrossRef]
44. Möller, S.; Palumbo, R. Solar thermal decomposition kinetics of ZnO in the temperature range 1950–2400 K.
Chem. Eng. Sci. 2001, 56, 4505–4515. [CrossRef]
45. Möller, S.; Palumbo, R. The development of a solar chemical reactor for the direct thermal dissociation of
zinc oxide. ASME J. Sol. Energy Eng. 2001, 123, 83–90. [CrossRef]
46. Abanades, S.; Charvin, P.; Flamant, G. Design and simulation of a solar chemical reactor for the thermal
reduction of metal oxides: Case study of zinc oxide dissociation. Chem. Eng. Sci. 2007, 62, 6323–6333.
[CrossRef]
47. Chambon, M.; Abanades, S.; Flamant, G. Design of a lab-scale rotary cavity-type solar reactor for continuous
thermal reduction of volatile oxides under reduced pressure. ASME J. Sol. Energy Eng. 2010, 132, 021006.
[CrossRef]
48. Chambon, M.; Abanades, S.; Flamant, G. Thermal dissociation of compressed ZnO and SnO2 powders in a
moving front solar thermochemical reactor. AIChE J. 2011, 57, 2264–2273. [CrossRef]
49. Chambon, M.; Abanades, S.; Flamant, G. Solar Thermal Reduction of ZnO and SnO2 : Characterization of the
Recombination Reaction with O2 . Chem. Eng. Sci. 2010, 65, 3671–3680. [CrossRef]
50. Levêque, G.; Abanades, S. Kinetic analysis of high-temperature solid–gas reactions by an inverse method
applied to ZnO and SnO2 solar thermal dissociation. Chem. Eng. J. 2013, 217, 139–149. [CrossRef]
51. Charvin, P.; Abanades, S.; Neveu, P.; Lemort, F.; Flamant, G. Dynamic modeling of a volumetric solar reactor
for volatile metal oxide reduction. Chem. Eng. Res. Design 2008, 86, 1216–1222. [CrossRef]
52. Schunk, L.O.; Steinfeld, A. Kinetics of the thermal dissociation of ZnO exposed to concentrated solar
irradiation using a solar-driven thermogravimeter in the 1800–2100 K range. AIChE J. 2009, 55, 1497–1504.
[CrossRef]
53. Perkins, C.; Lichty, P.; Weimer, A.W. Determination of aerosol kinetics of thermal ZnO dissociation by
thermogravimetry. Chem. Eng. Sci. 2007, 62, 5952–5962. [CrossRef]
54. Perkins, C.; Lichty, P.R.; Weimer, A.W. Thermal ZnO dissociation in a rapid aerosol reactor as part of a solar
hydrogen production cycle. Int. J. Hydrogen Energy 2008, 33, 499–510. [CrossRef]
55. Melchior, T.; Perkins, C.; Weimer, A.W.; Steinfeld, A. A cavity-receiver containing a tubular absorber for
high-temperature thermochemical processing using concentrated solar energy. Int. J. Therm. Sci. 2008, 47,
1496–1503. [CrossRef]
56. Haussener, S.; Hirsch, D.; Perkins, C.; Weimer, A.; Lewandowski, A.; Steinfeld, A. Modeling of a Multitube
High-Temperature Solar Thermochemical Reactor for Hydrogen Production. J. Sol. Energy Eng. 2009,
131, 024503. [CrossRef]
57. Haueter, P.; Moeller, S.; Palumbo, R.; Steinfeld, A. The production of zinc by thermal dissociation of zinc
oxide-Solar chemical reactor design. Sol. Energy 1999, 67, 161–167. [CrossRef]
58. Muller, R.; Haeberling, P.; Palumbo, R. Further advances toward the development of a direct heating solar
thermal chemical reactor for the thermal dissociation of ZnO(s). Sol. Energy 2006, 80, 500–511. [CrossRef]
59. Schunk, L.; Haeberling, P.; Wepf, S.; Wuillemin, D.; Meier, A.; Steinfeld, A. A Solar Receiver-Reactor for the
Thermal Dissociation of Zinc Oxide. ASME J. Sol. Energy Eng. 2008, 130, 021009. [CrossRef]
60. Koepf, E.; Villasmil, W.; Meier, A. Pilot-scale solar reactor operation and characterization for fuel production
via the Zn/ZnO thermochemical cycle. Appl. Energy 2016, 165, 1004–1023. [CrossRef]
61. Müller, R.; Steinfeld, A. H2 O-splitting thermochemical cycle based on ZnO/Zn-redox: Quenching the
effluents from the ZnO dissociation. Chem. Eng. Sci. 2008, 63, 217–227. [CrossRef]
62. Keunecke, M.; Meier, A.; Palumbo, R. Solar thermal decomposition of zinc oxide: An initial investigation
of the recombination reaction in the temperature range 1100–1250 K. Chem. Eng. Sci. 2004, 59, 2695–2704.
[CrossRef]
63. Berman, A.; Epstein, M. The kinetics of hydrogen production in the oxidation of liquid zinc with water vapor.
64. Wegner, K.; Ly, H.C.; Weiss, R.J.; Pratsinis, S.E.; Steinfeld, A. In situ formation and hydrolysis of Zn
nanoparticles for H2 production by the 2-step ZnO/Zn water-splitting thermochemical cycle. Int. J.
65. Weiss, R.J.; Ly, H.C.; Wegner, K.; Pratsinis, S.E.; Steinfeld, A. H2 production by Zn hydrolysis in a hot-wall
aerosol reactor. AIChE J. 2005, 51, 1966–1970. [CrossRef]
66. Ernst, F.O.; Tricoli, A.; Pratsinis, S.E.; Steinfeld, A. Co-synthesis of H2 and ZnO by in-situ Zn aerosol formation
and hydrolysis. AIChE J. 2006, 52, 3297–3303. [CrossRef]
67. Melchior, T.; Piatkowski, N.; Steinfeld, A. H2 production by steam-quenching of Zn vapor in a hot-wall
aerosol flow reactor. Chem. Eng. Sci. 2009, 64, 1095–1101. [CrossRef]
68. Abu Hamed, T.; Davidson, J.H.; Stolzenburg, M. Hydrolysis of Evaporated Zn in a Hot Wall Flow Reactor.
J. Sol. Energy Eng. 2008, 130, 041010. [CrossRef]
69. Lindemer, M.D.; Advani, S.G.; Prasad, A.K. Experimental investigation of heterogeneous hydrolysis with Zn
vapor under a temperature gradient. Int. J. Hydrogen Energy 2017, 42, 7847–7856. [CrossRef]
70. Weibel, D.; Jovanovic, Z.R.; Gálvez, E.; Steinfeld, A. Mechanism of Zn Particle Oxidation by H2 O and CO2 in
the Presence of ZnO. Chem. Mater. 2014, 26, 6486–6495. [CrossRef]
71. Ernst, F.O.; Steinfeld, A.; Pratsinis, S.E. Hydrolysis rate of submicron Zn particles for solar H2 synthesis.
72. Funke, H.H.; Diaz, H.; Liang, X.; Carney, C.S.; Weimer, A.W.; Li, P. Hydrogen generation by hydrolysis of
zinc powder aerosol. Int. J. Hydrogen Energy 2008, 33, 1127–1134. [CrossRef]
73. Vishnevetsky, I.; Epstein, M. Production of hydrogen from solar zinc in steam atmosphere. Int. J.
74. Abanades, S. Thermogravimetry analysis of CO2 and H2 O reduction from solar nanosized Zn powder for
thermochemical fuel production. Ind. Eng. Chem. Res. 2012, 51, 741–750. [CrossRef]
75. Villafán-Vidales, H.I.; Abanades, S.; Montiel-González, M.; Romero-Paredes, H.; Arancibia-Bulnes, C.A.;
Estrada, C.A. Transient heat transfer simulation of a 1 kWth moving front solar thermochemical reactor for
thermal dissociation of compressed ZnO. Chem. Eng. Res. Design 2015, 93, 174–184. [CrossRef]
76. Levêque, G.; Abanades, S. Investigation of thermal and carbothermal reduction of volatile oxides (ZnO,
SnO2 , GeO2 , and MgO) via solar-driven vacuum thermogravimetry for thermochemical production of solar
fuels. Thermochimica Acta 2015, 605, 86–94. [CrossRef]
77. Abanades, S.; Charvin, P.; Lemont, F.; Flamant, G. Novel two-step SnO2 /SnO water-splitting cycle for solar
thermochemical production of hydrogen. Int. J. Hydrogen Energy 2008, 33, 6021–6030. [CrossRef]
78. Charvin, P.; Abanades, S.; Lemont, F.; Flamant, G. Experimental study of SnO2 /SnO/Sn thermochemical
systems for solar production of hydrogen. AIChE J. 2008, 54, 2759–2767. [CrossRef]
79. Chambon, M.; Abanades, S.; Flamant, G. Kinetic investigation of hydrogen generation from hydrolysis of
SnO and Zn solar nanopowders. Int. J. Hydrogen Energy 2009, 34, 5326–5336. [CrossRef]
80. Abanades, S. CO2 and H2 O reduction by solar thermochemical looping using SnO2 /SnO redox reactions:
Thermogravimetric analysis. Int. J. Hydrogen Energy 2012, 37, 8223–8231. [CrossRef]
81. Levêque, G.; Abanades, S.; Jumas, J.-C.; Olivier-Fourcade, J. Characterization of two-step tin-based redox
system for thermochemical fuel production from solar-driven CO2 and H2 O splitting cycle. Ind. Eng.
Chem. Res. 2014, 53, 5668–5677. [CrossRef]
82. Levêque, G.; Abanades, S. Thermodynamic and kinetic study of the carbothermal reduction of SnO2 for
solar thermochemical fuel generation. Energy Fuels 2014, 28, 1396–1405. [CrossRef]
83. Sturzenegger, M.; Nuesch, P. Efficiency analysis for a manganese-oxide-based thermochemical cycle. Energy
1999, 24, 959–970. [CrossRef]
84. Abanades, S.; Flamant, G. Thermochemical hydrogen production from a two-step solar-driven water-splitting
cycle based on cerium oxides. Sol. Energy 2006, 80, 1611–1623. [CrossRef]
85. Charvin, P.; Abanades, S.; Bêche, E.; Lemont, F.; Flamant, G. Hydrogen production from mixed cerium oxides
via three-step water-splitting cycles. Solid State Ionics 2009, 180, 1003–1010. [CrossRef]
86. Bamberger, C.E.; Nichols, H. Basic chemistry of a new cycle, based on reactions of Ce(III) titanate, for splitting
water. Int. J. Hydrogen Energy 1979, 4, 513–516. [CrossRef]
87. Nakamura, T. Hydrogen production from water utilizing solar heat at high temperatures. Sol. Energy 1977,
19, 467–475. [CrossRef]
88. Sibieude, F.; Ducarroir, M.; Tofighi, A.; Ambriz, J. High temperature experiments with a solar furnace.
The decomposition of Fe3 O4 , Mn3 O4 , CdO. Int. J. Hydrogen Energy 1982, 7, 79–88. [CrossRef]
89. Tofighi, A.; Sibieude, F.; Ducarroir, M.; Benezech, G. Thermal decomposition of magnetite in air at the focus
of a solar furnace (Décomposition thermique à l’air de la magnétite au foyer d’un four solaire). Rev. Int. Htes
Temp. Réfract. 1978, 15, 7–14.
90. Tofighi, A.; Sibieude, F. Dissociation of magnetite in a solar furnace for hydrogen production. Tentative
production evaluation of a 1000 kW concentrator from small scale (2 kW) experimental results. Int. J.
91. Steinfeld, A.; Sanders, S.; Palumbo, R. Design aspects of solar thermochemical engineering—A case study:
Two-step water-splitting cycle using the Fe3 O4 /FeO redox system. Sol. Energy 1999, 65, 43–53. [CrossRef]
92. Weidenkaff, A.; Nüesch, P.; Wokaun, A.; Reller, A. Mechanistic studies of the water-splitting reaction for
producing solar hydrogen. Solid State Ionics 1997, 101–103, 915–922. [CrossRef]
93. Charvin, P.; Abanades, S.; Flamant, G.; Lemort, F. Two-step water-splitting thermochemical cycle based on
iron oxide redox pair for solar hydrogen production. Energy 2007, 32, 1124–1133. [CrossRef]
94. Charvin, P.; Abanades, S.; Lemort, F.; Flamant, G. Hydrogen production by three-step solar thermochemical
cycles using hydroxides and metal oxide systems. Energy Fuels 2007, 21, 2919–2928. [CrossRef]
95. Ehrensberger, K.; Frei, A.; Kuhn, P.; Oswald, H.; Hug, P. Comparative experimental investigations of the
water splitting reaction with iron oxide Fe1-y O and iron manganese oxides (Fe1-x Mnx )1-y O. Solid State Ionics
1995, 78, 151–160. [CrossRef]
96. Tamaura, Y.; Steinfeld, A.; Kuhn, P.; Ehrensberger, K. Production of solar hydrogen by a novel, 2-step,
water-splitting thermochemical cycle. Energy 1995, 20, 325–330. [CrossRef]
97. Tamaura, Y.; Ueda, Y.; Matsunami, J.; Hasegawa, N.; Nesuka, M.; Sano, T.; Tsuji, M. Solar hydrogen production
by using ferrites. Sol. Energy 1999, 65, 55–57. [CrossRef]
98. Tamaura, Y.; Kojima, M.; Sano, Y.; Ueda, Y.; Hasegawa, N.; Tsuji, M. Thermodynamic evaluation of water
splitting by a cation excessive (Ni, Mn) ferrite. Int. J. Hydrogen Energy 1998, 23, 1185–1191. [CrossRef]
99. Inoue, M.; Hasegawa, N.; Uehara, R.; Gokon, N.; Kaneko, H.; Tamaura, Y. Solar hydrogen generation with
H2 O/ZnO/MnFe2 O4 system. Sol. Energy 2004, 76, 309–315. [CrossRef]
100. Kaneko, H.; Hosokawa, Y.; Kojima, N.; Gokon, N.; Hasegawa, N.; Kitamura, M.; Tamaura, Y. Studies on
metal oxides suitable for enhancement of the O2 -releasing step in water splitting by the MnFe2 O4 –Na2 CO3
system. Energy 2001, 26, 919–929. [CrossRef]
101. Kaneko, H.; Hosokawa, Y.; Gokon, N.; Kojima, N.; Hasegawa, N.; Kitamura, M.; Tamaura, Y. Enhancement
of O2 -releasing step with Fe2 O3 in the water splitting by MnFe2 O4 –Na2 CO3 system. J. Phys. Chem. Solids
2001, 62, 1341–1347. [CrossRef]
102. Kaneko, H.; Ochiai, Y.; Shimizu, K.; Hosokawa, Y.; Gokon, N.; Tamaura, Y. Thermodynamic study based on
the phase diagram of the Na2 O–MnO–Fe2 O3 system for H2 production in three-step water splitting with
Na2 CO3 /MnFe2 O4 /Fe2 O3 . Sol. Energy 2002, 72, 377–383. [CrossRef]
103. Kaneko, H.; Gokon, N.; Hasegawa, N.; Tamaura, Y. Solar thermochemical process for hydrogen production
using ferrites. Energy 2005, 30, 2171–2178. [CrossRef]
104. Tamaura, Y.; Kojima, N.; Hasegawa, N.; Inoue, M.; Uehara, R.; Gokon, N.; Kaneko, H. Stoichiometric studies
of H2 generation reaction for H2 O/Zn/Fe3 O4 system. Int. J. Hydrogen Energy 2001, 26, 917–922. [CrossRef]
105. Tamaura, Y.; Kaneko, H. Oxygen-releasing step of ZnFe2 O4 /(ZnO + Fe3 O4 )-system in air using concentrated
solar energy for solar hydrogen production. Sol. Energy 2005, 78, 616–622. [CrossRef]
106. Takahashi, Y.; Aoki, H.; Kaneko, H.; Hasegawa, N.; Suzuki, A.; Tamaura, Y. Oxygen-gas-releasing reaction of
Zn ferrite by Xe lamp beam irradiation in air at 1800 K. Solid State Ionics 2004, 172, 89–91. [CrossRef]
107. Aoki, H.; Kaneko, H.; Hasegawa, N.; Ishihara, H.; Suzuki, A.; Tamaura, Y. The ZnFe2 O4 /(ZnO+Fe3 O4 ) system
for H2 production using concentrated solar energy. Solid State Ionics 2004, 172, 113–116. [CrossRef]
108. Tamaura, Y.; Uehara, R.; Hasegawa, N.; Kaneko, H.; Aoki, H. Study on solid-state chemistry of the
ZnO/Fe3 O4 /H2 O system for H2 production at 973–1073 K. Solid State Ionics 2004, 172, 121–124. [CrossRef]
109. Kaneko, H.; Kojima, N.; Hasegawa, N.; Inoue, M.; Uehara, R.; Gokon, N.; Tamaura, Y.; Sano, T. Reaction
mechanism of H2 generation for H2 O/Zn/Fe3 O4 system. Int. J. Hydrogen Energy 2002, 27, 1023–1028.
[CrossRef]
110. Kaneko, H.; Kodama, T.; Gokon, N.; Tamaura, Y.; Lovegrove, K.; Luzzi, A. Decomposition of Zn-ferrite for
O2 generation by concentrated solar radiation. Sol. Energy 2004, 76, 317–322. [CrossRef]
111. Ishihara, H.; Hasegawa, N.; Aoki, H.; Kaneko, H.; Suzuki, A.; Tamaura, Y. Two-step water splitting for H2
production with ZnII -MnII,III -FeIII spinel structure using concentrated solar heat. Solid States Ionics 2004, 172,
112. Ishihara, H.; Kaneko, H.; Hasegawa, N.; Tamaura, Y. Two-step water-splitting at 1273–1623 K using
yttria-stabilized zirconia-iron oxide solid solution via co-precipitation and solid-state reaction. Energy 2008,
33, 1788–1793. [CrossRef]
113. Kaneko, H.; Yokoyama, T.; Fuse, A.; Ishihara, H.; Hasegawa, N.; Tamaura, Y. Synthesis of new ferrite,
Al–Cu ferrite, and its oxygen deficiency for solar H2 generation from H2 O. Int. J. Hydrogen Energy 2006, 31,
2256–2265. [CrossRef]
114. Kodama, T.; Kondoh, Y.; Yamamoto, R.; Andou, H.; Satou, N. Thermochemical hydrogen production by a
redox system of ZrO2 -supported Co(II)-ferrite. Sol. Energy 2005, 78, 623–631. [CrossRef]
115. Kodama, T.; Gokon, N.; Yamamoto, R. Thermochemical two-step water splitting by ZrO2 -supported
Nix Fe3−x O4 for solar hydrogen production. Sol. Energy 2008, 82, 73–79. [CrossRef]
116. Gokon, N.; Murayama, H.; Umeda, J.; Hatamachi, T.; Kodama, T. Monoclinic zirconia-supported Fe3 O4 for
the two-step water-splitting thermochemical cycle at high thermal reduction temperatures of 1400–1600 ◦ C.
117. Gokon, N.; Murayama, H.; Nagasaki, A.; Kodama, T. Thermochemical two-step water splitting cycles by
monoclinic ZrO2 -supported NiFe2 O4 and Fe3 O4 powders and ceramic foam devices. Sol. Energy 2009, 83,
118. Gokon, N.; Hasegawa, T.; Takahashi, S.; Kodama, T. Thermochemical two-step water-splitting for hydrogen
production using Fe-YSZ particles and a ceramic foam device. Energy 2008, 33, 1407–1416. [CrossRef]
119. Gokon, N.; Takahashi, S.; Yamamoto, H.; Kodama, T. Thermochemical two-step water-splitting reactor with
internally circulating fluidized bed for thermal reduction of ferrite particles. Int. J. Hydrogen Energy 2008, 33,
2189–2199. [CrossRef]
120. Kaneko, H.; Miura, T.; Fuse, A.; Ishihara, H.; Taku, S.; Fukuzumi, H.; Naganuma, Y.; Tamaura, Y. Rotary-Type
Solar Reactor for Solar Hydrogen Production with Two-step Water Splitting Process. Energy Fuels 2007, 21,
2287–2293. [CrossRef]
121. Han, S.B.; Kang, T.B.; Joo, O.S.; Jung, K.D. Water splitting for hydrogen production with ferrites. Sol. Energy
2007, 81, 623–628. [CrossRef]
122. Roeb, M.; Sattler, C.; Klüser, R.; Monnerie, N.; de Oliveira, L.; Konstandopoulos, A.G.; Agrafiotis, C.;
Zaspalis, V.T.; Nalbandian, L.; Steele, A.; et al. Solar Hydrogen Production by a Two-Step Cycle Based on
Mixed Iron Oxides. J. Sol. Energy Eng. 2006, 128, 125–133. [CrossRef]
123. Roeb, M.; Neises, M.; Säck, J.-P.; Rietbrock, P.; Monnerie, N.; Dersch, J.; Schmitz, M.; Sattler, C. Operational
strategy of a two-step thermochemical process for solar hydrogen production. Int. J. Hydrogen Energy 2009,
34, 4537–4545. [CrossRef]
124. Agrafiotis, C.; Roeb, M.; Konstandopoulos, A.G.; Nalbandian, L.; Zaspalis, V.T.; Sattler, C.; Stobbe, P.;
Steele, A.M. Solar water splitting for hydrogen production with monolithic reactors. Sol. Energy 2005, 79,
125. Agrafiotis, C.C.; Pagkoura, C.; Lorentzou, S.; Kostoglou, M.; Konstandopoulos, A.G. Hydrogen production
in solar reactors. Catal. Today 2007, 127, 265–277. [CrossRef]
126. Diver, R.B.; Miller, J.E.; Allendorf, M.D.; Siegel, N.P.; Hogan, R.E. Solar Thermochemical Water-Splitting
Ferrite-Cycle Heat Engines. J. Sol. Energy Eng. 2008, 130, 041001. [CrossRef]
127. Allendorf, M.D.; Diver, R.B.; Siegel, N.P.; Miller, J.E. Two-Step Water Splitting Using Mixed-Metal Ferrites:
Thermodynamic Analysis and Characterization of Synthesized Materials. Energy Fuels 2008, 22, 4115–4124.
[CrossRef]
128. Fletcher, E.A. Solar thermal and solar quasi-electrolytic processing and separations: Zinc from zinc oxide as
an example. Ind. Eng. Chem. Res. 1999, 38, 2275–2282. [CrossRef]
129. Palumbo, R.D.; Fletcher, E.A. High-temperature solar electrothermal processing. Zinc from zinc-oxide at
1200–1675 K using a non-consumable anode. Energy 1988, 14, 319–332. [CrossRef]
130. Souriau, D. Procédé et Dispositif pour L’utilisation D’énergie Thermique à Haute Température, en Particulier
d’Origine Nucléaire. Device and Method for the Use of High-Temperature Heat Energy, in Particular of
Nuclear Origin. Gaz de France Patent FR2135421, 22 December 1972. (In French)
131. Vishnevetsky, I.; Epstein, M. Tin as a Possible Candidate for Solar Thermochemical Redox Process for
Hydrogen Production. J. Sol. Energy Eng. 2009, 131, 021007. [CrossRef]
132. Fletcher, E.A. Solar thermal processing: A review. J. Sol. Energy Eng. 2001, 123, 63–74. [CrossRef]
133. Kodama, T. High-temperature solar chemistry for converting solar heat to chemical fuels. Prog. Energy
Combust. Sci. 2003, 29, 567–597. [CrossRef]
134. Segal, A.; Epstein, M. The optics of the solar tower reflector. Sol. Energy 2000, 69, 229–241. [CrossRef]
135. Kaneko, H.; Miura, T.; Ishihara, H.; Taku, S.; Yokoyama, T.; Nakajima, H.; Tamaura, Y. Reactive ceramics of
CeO2 -MOx (M = Mn, Fe, Ni, Cu) for H2 generation by two-step water splitting using concentrated solar
thermal energy. Energy 2007, 32, 656–663. [CrossRef]
136. Abanades, S.; Legal, A.; Cordier, A.; Peraudeau, G.; Flamant, G.; Julbe, A. Investigation of reactive
cerium-based oxides for H2 production by thermochemical 2-step water-splitting. J. Mater. Sci. 2010, 45,
4163–4173. [CrossRef]
137. Miller, J.E.; Allendorf, M.D.; Diver, R.B.; Evans, L.R.; Siegel, N.P.; Stuecker, J.N. Metal oxide composites
and structures for ultra-high temperature solar thermochemical cycles. J. Mater. Sci. 2008, 43, 4714–4728.
[CrossRef]
138. Chueh, W.; Haile, S.M. A thermochemical study of ceria: Exploiting an old material for new modes of energy
conversion and CO2 mitigation. Phil. Trans. R. Soc. A 2010, 368, 3269–3294. [CrossRef]
139. Chueh, W.C.; Haile, S.M. Ceria as a Thermochemical Reaction Medium for Selectively Generating Syngas or
Methane from H2 O and CO2 . ChemSusChem 2009, 12, 735–739. [CrossRef]
140. Kaneko, H.; Tamaura, Y. Reactivity and XAFS study on (1−x)CeO2 –xNiO (x = 0.025–0.3) system in the
two-step water-splitting reaction for solar H2 production. J. Phys. Chem. Solids 2009, 70, 1008–1014. [CrossRef]
141. Kaneko, H.; Ishihara, H.; Taku, S.; Naganuma, Y.; Hasegawa, N.; Tamaura, Y. Cerium ion redox system in
CeO2 –xFe2 O3 solid solution at high temperatures (1,273–1,673 K) in the two-step water-splitting reaction for
solar H2 generation. J. Mater. Sci. 2008, 43, 3153–3161. [CrossRef]
142. Meng, Q.-L.; Lee, C.-I.; Ishihara, T.; Kaneko, H.; Tamaura, Y. Reactivity of CeO2 based ceramics for solar
hydrogen production via a two-step water-splitting cycle with concentrated energy. Int. J. Hydrogen Energy
2011, 36, 13435–13441. [CrossRef]
143. Kaneko, H.; Taku, S.; Tamaura, Y. Reduction reactivity of CeO2 -ZrO2 oxide under high O2 partial pressure in
two-step water-splitting process. Sol. Energy 2011, 85, 2321–2330. [CrossRef]
144. Lee, C.; Meng, Q.; Kaneko, H.; Tamaura, Y. Solar hydrogen productivity of ceria-scandia solid solution using
two-step water-splitting cycle. J. Sol. Energy Eng. 2013, 135, 11002–11009. [CrossRef]
145. Le Gal, A.; Abanades, S. Catalytic investigation of ceria-zirconia solid solutions for solar hydrogen production.
146. Le Gal, A.; Abanades, S.; Flamant, G. CO2 and H2 O splitting for thermochemical production of solar fuels
using non-stoichiometric ceria and ceria/zirconia solid solutions. Energy Fuels 2011, 25, 4836–4845. [CrossRef]
147. Le Gal, A.; Abanades, S. Dopant incorporation in ceria for enhanced water-splitting activity during solar
thermochemical hydrogen generation. J. Phys. Chem. C 2012, 116, 13516–13523. [CrossRef]
148. Abanades, S.; Le Gal, A. CO2 splitting by thermo-chemical looping based on Zrx Ce1-x O2 oxygen carriers for
synthetic fuel generation. Fuel 2012, 102, 180–186. [CrossRef]
149. Le Gal, A.; Abanades, S.; Bion, N.; Le Mercier, T.; Harlé, V. Reactivity of Doped Ceria-Based Mixed Oxides
for Solar Thermochemical Hydrogen Generation via Two-Step Water-Splitting Cycles. Energy Fuels 2013, 27,
6068–6078. [CrossRef]
150. Call, F.; Roeb, M.; Schmücker, M.; Sattler, C.; Pitz-Paal, R. Ceria Doped with Zirconium and Lanthanide
Oxides to Enhance Solar Thermochemical Production of Fuels. J. Phys. Chem. C 2015, 119, 6929–6938.
[CrossRef]
151. Bulfin, B.; Call, F.; Vieten, J.; Roeb, M.; Sattler, C.; Shvets, I.V. Oxidation and Reduction Reaction Kinetics of
Mixed Cerium Zirconium Oxides. J. Phys. Chem. C 2016, 120, 2027–2035. [CrossRef]
152. Muhich, C.; Hoes, M.; Steinfeld, A. Mimicking tetravalent dopant behavior using paired charge compensating
dopants to improve the redox performance of ceria for thermochemically splitting H2 O and CO2 .
Acta Materialia 2018, 144, 728–737. [CrossRef]
153. Davenport, T.C.; Kemei, M.; Ignatowich, M.J.; Haile, S.M. Interplay of material thermodynamics and surface
reaction rate on the kinetics of thermochemical hydrogen production. Int. J. Hydrogen Energy 2017, 42,
16932–16945. [CrossRef]
154. Petkovich, N.D.; Rudisill, G.; Ventrom, L.J.; Bomant, D.B.; Davidson, J.H.; Stein, A. Control of heterogeneity
in nanostructured Ce1−x Zrx O2 binary oxides for enhanced thermal stability and water splitting activity.
J. Phys. Chem. C 2011, 115, 21022–21033. [CrossRef]
155. Oliveira, F.A.C.; Barreiros, M.A.; Abanades, S.; Caetano, A.P.F.; Novais, R.M.; Pullar, R.C. Solar
thermochemical CO2 splitting using cork-templated ceria ecoceramics. J. CO2 Util. 2018, 26, 552–563.
[CrossRef]
156. Furler, P.; Scheffe, J.R.; Steinfeld, A. Syngas production by simultaneous splitting of H2 O and CO2 via ceria
redox reactions in a high-temperature solar reactor. Energy Environ. Sci. 2012, 5, 6098–6103. [CrossRef]
157. Gladen, A.C.; Davidson, J.H. The morphological stability and fuel production of commercial fibrous ceria
particles for solar thermochemical redox cycling. Sol. Energy 2016, 139, 524–532. [CrossRef]
158. Furler, P.; Scheffe, J.; Gorbar, M.; Moes, L.; Vogt, U.; Steinfeld, A. Solar thermochemical CO2 splitting utilizing
a reticulated porous ceria redox system. Energy Fuels 2012, 26, 7051–7059. [CrossRef]
159. Marxer, D.; Furler, P.; Takacs, M.; Steinfeld, A. Solar thermochemical splitting of CO2 into separate streams of
CO and O2 with high selectivity, stability, conversion, and efficiency. Energy Environ. Sci. 2017, 10, 1142–1149.
[CrossRef]
160. Cho, H.S.; Gokon, N.; Kodama, T.; Kang, Y.H.; Lee, H.J. Improved operation of solar reactor for two-step
water-splitting H2 production by ceria-coated ceramic foam device. Int. J. Hydrogen Energy. 2015, 40, 114–124.
[CrossRef]
161. Scheffe, J.R.; Steinfeld, A. Oxygen exchange materials for solar thermochemical splitting of H2 O and CO2 :
A review. Mater. Today 2014, 17, 341–348. [CrossRef]
162. Carrillo, R.J.; Scheffe, J.R. Advances and trends in redox materials for solar thermochemical fuel production.
Sol. Energy 2017, 156, 3–20. [CrossRef]
163. Roeb, M.; Neises, M.; Monnerie, N.; Call, F.; Simon, H.; Sattler, C.; Schmücker, M.; Pitz-Paal, R.
Materials-Related Aspects of Thermochemical Water and Carbon Dioxide Splitting: A Review. Materials
2012, 5, 2015–2054. [CrossRef]
164. Scheffe, J.R.; Weibel, D.; Steinfeld, A. Lanthanum-strontium-manganese perovskites as redox materials for
solar thermochemical splitting of H2 O and CO2 . Energy Fuels 2013, 27, 4250–4257. [CrossRef]
165. McDaniel, A.H.; Miller, E.C.; Arifin, D.; Ambrosini, A.; Coker, E.N.; O’Hayre, R.; Chueh, W.C.; Tong, J. Sr-
and Mn-doped LaAlO3 -delta for solar thermochemical H2 and CO production. Energy Environ. Sci. 2013, 6,
2424–2428. [CrossRef]
166. Demont, A.; Abanades, S.; Beche, E. Investigation of perovskite structures as oxygen-exchange redox
materials for hydrogen production from thermochemical two-step water-splitting cycles. J. Phys. Chem. C
2014, 118, 12682–12692. [CrossRef]
167. Yang, C.-K.; Yamazaki, Y.; Aydin, A.; Haile, S.M. Thermodynamic and kinetic assessments of strontium-doped
lanthanum manganite perovskites for two-step thermochemical water splitting. J. Mater. Chem. A 2014, 2,
13612–13623. [CrossRef]
168. Demont, A.; Abanades, S. High redox activity of Sr-substituted lanthanum manganite perovskites for
two-step thermochemical dissociation of CO2 . RSC Adv. 2014, 4, 54885–54891. [CrossRef]
169. Demont, A.; Abanades, S. Solar thermochemical conversion of CO2 into fuel via two-step redox cycling of
non-stoichiometric Mn-containing perovskite oxides. J. Mater. Chem. A 2015, 3, 3536–3546. [CrossRef]
170. Nair, M.M.; Abanades, S. Insights into the Redox Performance of Non-stoichiometric Lanthanum Manganite
Perovskites for Solar Thermochemical CO2 Splitting. ChemistrySelect 2016, 1, 4449–4457. [CrossRef]
171. Nair, M.M.; Abanades, S. Experimental screening of perovskite oxides as efficient redox materials for solar
thermochemical CO2 conversion. Sustain. Energy Fuels 2018, 2, 843–854. [CrossRef]
172. Orfila, M.; Linares, M.; Molina, R.; Botas, J.A.; Sanz, R.; Marugan, J. Perovskite materials for hydrogen
production by thermochemical water splitting. Int. J. Hydrogen Energy 2016, 41, 19329–19338. [CrossRef]
173. Haeussler, A.; Abanades, S.; Jouannaux, J.; Julbe, A. Non-stoichiometric redox active perovskite materials for
solar thermochemical fuel production: A review. Catalysts 2018, 8, 611. [CrossRef]
© 2019 by the author. Licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
(CC BY) license (http://creativecommons.org/licenses/by/4.0/).

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ChemEngineering 2019, 3, 63; doi:10.3390/chemengineering3030063 www.mdpi.com/journal/chemengineering

ChemEngineering 2019, 3, x FOR PEER REVIEW 3 of 28

2. Volatile Metal Oxide Cycles

2.1. ZnO/Zn Cycle

Figure 3. Evolution of chemical conversion during SnO nanoparticles hydrolysis at different

Figure 8. SEM images solar-produced

-15 Towards FeO

3 ZnO + 2 Fe3 O4 + H2 O → 3 ZnFe2 O4 + H2 T = 600–8000 ◦ C (7)

x/3Fe3 O4 + Yy Zr1−y O2−y/2 → Fe2+ x Yy Zr1−y O2−y/2+x + x/6O2 (9)

Fe2+ x Yy Zr1−y O2−y/2+x + x/2H2 O → Fe3+ x Yy Zr1−y O2−y/2+3x/2 + x/2H2 (10)

Fe3+ x Yy Zr1−y O2−y/2+3x/2 → Fe2+ x Yy Zr1−y O2−y/2+x + x/4O2 (11)

In parallel to the fundamental research on the abovementioned redox working materials,

ChemEngineering 2019, 3, x FOR PEER REVIEW 19 of 28

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